纸和纸板材料具有使用历史悠久、原材料来源丰富、质轻和易加工等优点,被广泛应用于食品等消费品的包装和保护。由于天然多孔纸材料的耐液体性、稳定性和耐化学迁移性较差,在造纸加工过程中会添加多种功能助剂以改善其使用性能,其中包括全氟或多氟烷基化合物(per- and polyfluoroalkyl substances, PFASs)[1]。PFASs是一类人工合成的化学物质,因其具有典型的疏水、疏油结构,PFASs通常可以用于多种工业产品并改善其使用性能,如纺织品、食品包装、消防泡沫等[2]。随着分析技术的进步,PFASs被发现广泛存在于环境、消费品甚至人体中。PFASs结构中的C—F键具有高化学稳定性,其因此表现出的较为缓慢的生物、环境降解特性以及生物蓄积性,使其成了全球范围内高度关注的永久性污染物[3]。

对于食品接触用纸,添加PFASs及其助剂可以有效提高纸张的疏水疏油、耐高温等性能。然而,这类经过PFASs处理的纸制品与食品接触可能会引起潜在的人类健康问题[4]。随着对食品安全要求的日益严格,传统含PFASs的添加助剂或产品正逐步受到管控和替代,但与此同时更多未知的新型PFASs物质被不断发现[5-6]。持续增长的新型PFASs意味着未来逐渐增大的人体暴露和食品安全风险。本文首先梳理介绍了PFASs的主要类别及其毒性危害,然后从食品接触用纸的角度,归纳了PFASs的潜在来源、暴露污染和健康风险,并总结和整理了食品接触用纸中PFASs的监管法规以及检测研究进展,旨在对食品接触用纸和食品中这类新污染物的了解、研究和监管提供参考。

1 PFASs的类别和毒性危害

1.1 主要类别

全氟或多氟烷基化合物是至少含有一个完全氟化碳原子(—CF2—、—CF3—)、高度氟化的脂肪族物质总称[7]。除了完全或部分氟化的烷基链之外,这类物质的结构中通常还存在包括羧酸、磺胺、羟基等末端基团[6],见表1。

由于结构的高度多样化,PFASs物质通常可分为聚合物和非聚合物两类。非聚合类PFASs包括完全氟化的全氟烷基酸(perfluoroalkyl acids, PFAAs)和以PFAAs前体物为代表的多氟烷基化合物[2, 8]。此外,按照烷基结构末端官能团的类型,PFAAs可分为全氟烷基羧酸(perfluoroalkyl carboxy-lic acids, PFCAs)、全氟烷基磺酸(perfluoroalkane sulfonic acids, PFSAs)、全氟烷基磷酸(perfluoroalkane sulfonic acids, PFPAs)等多种亚类阴离子PFASs,例如广泛受到关注的全氟辛酸(perfluorooctanoic acid, PFOA)、全氟辛烷磺酸(perfluorooctane sulfonic acid, PFOS)、全氟己烷磺酸(perfluorohexane sulfonic acid, PFHxS)等。而在PFAAs前体物中主要包含了非离子化氟调聚醇(fluorotelomer alcohols, FTOHs)、多氟烷基磷酸酯(polyfluoroalkyl phosphate esters, PAPs)、氟调聚羧酸(fluorotelomer carboxylic acids, FTCAs)、氟调聚磺酸(fluorotelomer sulfonic acids, FTSAs)等。不同类别PFAAs前体物分别代表了多种PFAS物质,如5∶3 FTCA物质碳链结构中有5个被氟原子部分取代或完全取代的甲基或亚甲基,其余3个甲基或亚甲基没有被氟原子取代。以聚合物形式存在的PFASs主要是PFPEs和由多个PFASs聚合而成的含氟聚合物[2, 8]。除此之外,若根据氟链段结构上碳原子的数目,PFASs还可以简单地划分为碳原子数量大于7个的长链PFASs和其余的短链PFASs[9]。如PFOS、PFOA是碳原子数量等于8的长链PFAAs,也是众多环境污染、食品或包装材料安全等有关研究和法规监管中重点关注的物质[10]。

1.2 毒性危害

摄入人体的PFASs会对人体健康产生严重危害,这主要与PFASs表现出的极强生物蓄积性等特征有关。相较于脂肪组织,PFASs很容易与血清蛋白和其他胞浆蛋白等结合,从而富集在人体血液、肝脏、肾脏等部位中[11-13]。研究表明,PFOA、PFOS在人体血液中的半衰期分别可长达1.5年和4.8年[14-15]。有关研究表明,也在母乳[13]、脐带血[16]中检出了PFASs。流行病学调查表明,PFASs与肾癌等多种癌症有着密切联系[17],并且产前暴露于PFASs会对孕妇和新生儿的甲状腺功能造成破坏[18]。基于动物毒理试验的研究表明,PFASs会对多个器官产生直接或间接的毒性作用,比如神经毒性[19]、生殖及发育毒性[20]、代谢毒性[21]等。相关研究发现,传统PFCAs、PFSAs等表现出肝毒性[22],人体血清中PFBA浓度的升高会导致新冠病毒感染后的症状更严重[23]。此外,除了广泛关注的传统PFASs物质,新型的PFASs替代物也被发现具有较高的毒性和危害。如毒理学试验表明PAPs、FTOHs的人体摄入会抑制雄性激素的合成,造成潜在的生殖毒性和发育毒性[24-25]。然而,更多新型种类PFASs的危害和毒性机理仍有待深入探索和评估。

2 PFASs的来源和膳食暴露

2.1 来源情况

原纸纤维有交叉多孔特性,在实际造纸或制品成型等生产阶段中一般会有意添加化学助剂帮助改善产品的使用性能。PFASs及其助剂可以通过内部添加或外部浸渍、施胶或表面涂层等方式赋予纸制品更丰富的功能和特性,如防水、防油、耐高温等[1, 26]。非聚合类PFASs通常可以用于改善纸和纸板材料的防油、防水和不粘性。向造纸纤维浆中添加含氟表面活性剂,比如二烷基多氟磷酸酯表面活性剂diPAPs等,可以加强造纸纤维之间的紧密程度,并且PFASs极性基团与纤维素相互结合后,暴露在外侧的疏水基团可以为制品提供防油防水性能[1]。含氟聚合物同样可以被添加到或用作纸和纸板的涂层材料,同样能够赋予纸制品优良的防水防油性能,比如含有FTOHs或PAPs等氟侧链的多氟丙烯酸酯类聚合物涂层[8]。

此外,纸和纸板材料中还可能出现其他非有意添加的PFASs。例如,在纸和纸板制造过程中的氟化处理会导致PFASs的残留[2, 26]。在大气氧化或生物降解作用下,部分有意添加的FTOHs、PAPs等可能降解产生FTCAs,进而转化为各种PFCAs、PFSAs,比如常见的PFOA、PFOS等[5,27]。外部环境污染,比如造纸用水、纤维原料污染,也会导致纸和纸板材料中PFASs污染[28]。

2.2 污染情况

经PFASs处理的纸基材料往往都具有优良的防水、防油或耐高温性能,通常被用来制造加工防油纸袋、一次性纸盘、纸杯等制品。大量研究表明,在这类纸制品中容易观察到不同程度的PFASs污染。例如,Monge等[28]分析发现在传统快餐纸包装中存在可检出的PFOA、PFOS残留。Poothong等[29]也同样发现在微波加热爆米花纸袋、冰淇淋纸筒等制品中也存在传统的PFOA、PFOS等PFASs。

尽管PFOA、PFOS等物质逐步被替代,但食品接触用纸中依旧可能存在传统PFASs的安全隐患。此外,随着传统PFASs的替代物的出现和应用,在食品接触用纸中也逐渐发现更多其他长链PFASs及其前体物的污染。例如,Sapozhnikova等[30]从不同国家和地区收集的食品接触材料中检出了多种PFASs污染物,其中diPAPs、PFDA和短链PFHpA、PFPeA、PFHxS的检出频率较高。Chen等[31]重点调查了国内食品接触用纸中PFASs的污染情况,从爆米花纸袋、植物基餐具、烘焙纸等食品接触纸中不同程度地检出了PFCAs、FTCAs和FTUCAs等26种PFASs。Zabaleta等[32]全面筛查了从多个国家收集的爆米花纸袋,发现在欧盟等地区纸样中主要检出短链PFCAs及其前体物,而在亚洲地区的纸样中主要检测到长链PFCAs。

此外,甘蔗浆等植物纤维基环保纸制品中也可能会有意使用含PFASs的防水防油助剂以及施胶剂等,从而导致PFASs污染。例如,Yuan等[33]研究了从美国、中国收集的多种纸制品,在植物基纸餐具、爆米花纸袋中识别了多种新型长链FTOHs,并且FTOHs总残留量明显较高。这些研究都表明,不同国家和地区的纸样中存在不同程度的PFASs污染,这与各国、各地区对禁止使用和生产PFASs的监管力度等因素有关[29, 33]。除了已被鉴定和研究的传统或新型PFASs,食品接触用纸中还存在更多亟待识别的PFASs[34-35]。

2.3 膳食暴露

由于PFASs广泛存在于环境中,人们接触到这类污染物的潜在途径比较复杂,比如皮肤接触[36]、手部摩擦[37]、空气传播等,但是大量研究表明,摄入被污染的食品、水等饮食是PFASs出现生物累积、进入食物链并暴露于人体的主要途径[38-42]。欧洲食品安全局食物链污染物小组调查发现了不同种类的食品都可能存在PFASs污染,比如鱼类[43]、蔬菜[44-45]等,会对消费者健康产生潜在威胁[46]。

食品接触用纸与不同种类食品接触时,潜在的PFASs可能会迁移到食品之中,然后通过饮食摄入暴露于人体并导致其在消费者饮食中的安全问题[30, 33]。例如,Still等[47]发现经包装后的乳制品中会检测到PFCAs、FTOHs等残留。Lerch等[48]发现一次性纸盘等纸制品中PFCAs、FTOHs等多种亚类PFASs会迁移到酒精性食品模拟物和松饼、燕麦粥、番茄汤等饮食中,评估发现通过酒精性食品摄入到人体的短链PFHxA、6∶2 FTOH等会危害到消费者健康。Chen等[31]也调查发现爆米花纸袋等制品中FTCAs、PFCAs等会迁移到酒精性食品模拟物,构成人类健康风险。

食品接触用纸中PFASs向食品中的迁移会受到接触温度、接触时间、食品性质等多种因素的影响[27, 49]。随着迁移时间的增加或迁移温度的升高,PFASs向食品的迁移会更加显著。例如,研究发现相较于80 ℃,在120 ℃下从防油纸袋包装中迁移到奶粉中的PFCAs、迁移到低脂牛奶中的PFHxPA等均会明显增多[50]。Zabaleta等[51]研究发现在室温下将迁移时间从20 min延长至30 min会导致迁移到50%乙醇食品模拟物中的PFHpA含量增加20%。Chen等[31]发现随着接触时间增加,从防油纸袋中迁移到50%乙醇中的PFCAs、FTCAs也会呈现增加趋势。因此,对于传统的快餐类食品接触用纸,尤其是在高温条件下使用的防油纸袋、纸盘等,其潜在的PFASs暴露和风险问题仍需要重点关注[31, 51-53]。

此外,食品接触用纸中PFASs的迁移行为与接触食品性质等有关,比如脂肪含量、水含量、pH值等。PFASs更容易迁移到高脂肪、高蛋白质的食品中,并且食品中的乳化剂会使得PFASs更易与食品结合[27, 54-55]。例如,Elizalde等[50]发现从纸袋中迁移到全脂牛奶中的PFOA、PFDA、PFHxPA等物质含量明显高于迁移到低脂牛奶中的含量。食品中添加的大豆卵磷脂、吐温60会显著增加PFASs的迁移[53]。Fengler等[56]通过对比防油纸向不同配方松饼中的迁移,发现高水分含量会抑制PFASs在食品中的吸收。相较于真实食品或酒精性食品,PFASs在水性、酸性食品中的迁移率明显更低[31,33,54]。当采用Tenax®作为谷物、大米和奶粉等食品的替代模拟物进行研究时,随着食品脂肪含量增大、PFSAs氟化碳链长度的减少,其结果可能会低于PFASs的真实迁移水平[50-51]。

3 对PFASs的管控和限量要求

在预期的使用条件下,从食品接触用纸迁移到食品中的化学物质不得对食品质量或风味产生不利影响,也不得引起潜在的安全问题[57]。考虑到PFASs表现出的毒性和高危害性,众多国家和地区的相关组织加强了对这类污染物的管控。从2023年3月起,中国明确禁止了PFOS、PFOA、PFHxS等及其相关化合物在非特定工业用途下的生产和加工使用[58]。根据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》可知,中国法规采用了正向清单管理,未授权的PFASs不得在食品接触材料中添加使用或检出。在欧盟,多个代表性PFASs同时被列入了高度关注物质(substances of very high concern, SVHC)清单,这意味着这些物质在加工和生产使用中也会受到重点监管和限制,包括PFOA、PFOS、PFBS、PFHxS及其盐类等。不同国家或地区对食品接触用纸和纸板中PFASs的限量要求见表2。

由表2可知,欧盟EU 2019/1021持久性有机污染物(persistent organic pollutants, POPs)法规规定,食品包装中PFOA、PFHxS及其盐类物质残留量不得超过0.025 mg/kg、PFOA和PFHxS相关物质含量不得超过1.0 mg/kg。在欧盟(EC)1907/2006 REACH 法规附录XVII 修正提案中规定除聚合态PFASs之外,PFASs总量不超过0.25 mg/kg、包括聚合态PFASs在内的总氟含量不得超过50 mg/kg。此外,丹麦第681/202号行政命令明确规定从2020年7月开始,禁止食品接触用纸和纸板材料及其制品中添加使用PFASs,同时规定其中有机氟化合物总量应小于20 mg/kg,而美国加州议会法案AB 1200法规限制了食品包装中总有机氟含量不得超过100 mg/kg。

4 对PFASs的筛查和检测分析

4.1 靶向PFASs的定量分析

液相色谱-质谱联用(liquid chromatography-mass spectrometry, LC-MS)是用于分析PFASs的主要仪器,结合不同的样品前处理等可以实现对食品接触用纸中特定的PFASs的定量检测[6, 59]。例如,Begley等[54]采用液相色谱-质谱联用,结合50%乙醇溶剂萃取、分离纯化等样品处理方法,定量分析了纸样中的PFOA残留量和迁移量。Chen等[31]使用甲醇作为超声提取的溶剂,结合超高效液相色谱串联质谱(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS)同时分析了防油纸等样品中57种靶向PFASs,检测限和定量限分别能达到0.003～1.99 ng/g和0.01～6.62 ng/g。此外,PFASs可分为离子化物质和非离子化物质,部分研究针对性地开发了衍生化处理后气相色谱-化学电离质谱联用(gas chromatography-chemical ionization-mass spectrometry, GC-CI-MS)的方法,可以有效分析FTOHs等非离子化PFASs[47,56, 60]。然而,相较于LC-MS,这种方法的分析和衍生化前处理比较费时间。

4.2 氟含量筛查

考虑到PFASs的多样性,在缺乏标准物质的情况下,无法对未鉴定的PFASs进行定量分析。采用总可氧化前体测定(total oxidisable precursors assay, TOPA)可以将未知的PFAAs前体物转化成可检测的PFASs,随后进行靶向定量或筛查分析[30, 61-62]。此外,PFASs结构中均含有大量的氟原子,使用非特异性的仪器方法、氟质量平衡等方法可以定量分析氟化物含量,以快速筛查纸样中是否含有潜在的PFASs [62-64]。

取决于不同的样品类型和前处理方式,已有众多仪器、方法被应用于包装材料中氟含量的研究,如核磁共振、粒子诱导γ射线发射光谱法(particle-induced γ-ray emission spectroscopy, PIGE)[65]、燃烧离子色谱(combustion ion chromatography, CIC)[66]、仪器中子活化分析(instrumental neutron activation analysis, INAA)[63]、氟离子选择电极法(fluorine-ion selective electrode, F-ISE)[67]和电感耦合等离子体串联质谱法等。Schaider等[35]采用PIGE快速筛查了400多种食品接触用纸和纸板中的总氟含量,发现超过一半纸样具有较高的氟化物总量,表明存在未知的PFASs。Ignacio等[67]采用F-ISE测定分析了多种食品接触材料中总氟、总有机氟含量。Schultes等[63]采用PIGE、INAA和CIC三种方法共同验证分析了食品接触材料中总氟、乙醇提取有机氟含量的分布情况,通过氟质量平衡分析发现可提取出的有机氟含量、靶向PFASs总量分别仅占总氟、可提取有机氟含量的极小部分。除了已知或可量化的PFASs物质,那些未量化或不可提取的有机氟化物同样有待深入识别和研究。

由表2可知,总氟、总有机氟含量在国外被应用于食品接触用纸中PFASs的监管,但中国尚未规定参考的总氟、总有机氟限量。国内相关组织和机构共同制定了食品接触用纸中总氟[68]、总有机氟[69]和可提取有机氟含量[70]测定方法团体标准,这也是首次为国内纸和纸制品行业管控PFASs提供了的技术手段,将进一步促进食品接触用纸中PFASs的安全管控。

4.3 未知PFASs的非靶向分析

目前,已被识别和鉴定的PFASs已达5 000多种[71]。随着PFASs替代物被生产和使用,更多新型PFASs受到了广泛的关注[72]。通过高分辨质谱(high resolution mass spectrometry, HRMS)全扫描可以获取分辨率更高、更加准确的碎片质量数和全扫描灵敏度,能够帮助对关键质量数和物质碎片离子进行识别和推测,并分配物质的分子式和结构式,最后对分析候选物进行确认验证,比如串联质谱、四极杆飞行时间质谱、Orbitrap等[73-75]。

因此,基于HRMS的PFASs非靶向筛查也成了该领域的研究热点方向,并且部分研究将靶向PFASs分析、氟含量筛查和PFASs非靶向筛查等方法相互结合,用于对PFASs的综合分析[62]。例如,Chen等[31]采用超高效液相色谱串联四极杆飞行时间质谱(ultra performance liquid chromatography-time-of-flight mass spectrometry, UPLC-TOF-MS)同时实现了对食品接触用纸中靶向PFASs、潜在PFASs的定量和筛查分析,并且鉴定出9∶3 FTCA、11∶3 FTCA等多种新型PFASs。类似地,Zabaleta等[51]采用UPLC-TOF-MS在爆米花纸袋中鉴定发现了8∶2 FTCA、9∶3 FTCA等PFASs中间体。Sapozhnikova等[30]采用TOPA、UPLC-MS/MS、UPLC-Q-Orbitrap综合分析了多种类型食品接触材料中的PFASs,证明了潜在的PFASs前体物质的存在,并鉴定识别了6∶2 diPAP等物质。采用GC-HRMS同样可以非靶向鉴定那些未知的非离子化PFASs,比如水样中的PFASs[76],但该方法尚未应用到食品接触用纸等包装材料中PFASs的筛查分析。

5 总结与展望

纸和纸板材料具有质轻、易加工等特点,被广泛应用于多种类型食品的包装。然而,可能存在的PFASs污染会对人体健康产生潜在威胁。PFASs可以通过浸渍、施胶或表面涂层等方式被有意添加到纸板材料中,赋予制品更加优良的防水、防油和耐高温性能,尤其是传统快餐类防油纸袋、爆米花纸袋等制品。造纸用水等外部环境污染也可能导致食品接触用纸中非有意的PFASs污染。食品接触用纸与不同类别食品接触时,PFASs污染物可能会迁移到食品中,并通过饮食摄入暴露于人体,进而严重危害人体健康。目前,多个国家或地区都对PFASs污染物进行了管控,但不同地区的监管范围和力度有所不同。随着传统PFASs逐步被替代,更多新型的PFASs仍有待被鉴定和研究,因此未来的食品接触用纸中PFASs研究会逐渐侧重于更加全面的评估,即靶向PFASs定量分析、氟含量筛查、非靶向筛查和氟质量平衡分析等相互结合,以此提供更加可靠的PFASs鉴定和分析。同时,亟待进一步研究食品接触用纸中未知PFASs的来源、分布及其毒性危害,以帮助相关监管法规的建立和完善。

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Research Progress on Source, Limitation and Detection Technology of Per- and Polyfluoroalkyl Substances in Food Contact Paper

LIN Qinbao1, YANG Qinghua1,2, ZHAO Dan1, LU Shiqiang3, MA Hongsheng3

(1. College of Packaging Engineering, Jinan University, Zhuhai 519000, China;2. ZhiLi Technology (Guangdong) Co. Ltd., Guangzhou 510000, China;3. Zhuhai Hongta Renheng Packaging Co. Ltd., Zhuhai 519000, China)

Abstract：Per- and polyfluoroalkyl substances (PFASs) were a class of synthetic chemicals widely used in industrial products and consumer products. Due to their structural diversity and bioaccumulation properties, PFASs were recognized as highly concerned persistent pollutants. PFASs in food contact paper could contaminate food and endanger consumer health. There were various categories of PFASs, usually divided into polymers and non-polymers categories. Non-polymeric PFASs included perfluoroalkyl acids (PFAAs) and their precursors, while polymeric PFASs were mainly perfluoropolyethers (PFPEs) and fluoropolymers polymerized by multiple PFASs. According to the number of carbon atoms in the fluorine segment structure, PFASs were divided into long-chain PFASs with more than 7 carbon atoms and short-chain PFASs. Among them, common perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were long-chain PFAAs, which were the key substances in research and regulatory supervision. In food contact paper, PFASs came from a wide range of sources, which were not only intentionally added through impregnation, sizing, or coating to improve the performance of paper products but also unintentional addition caused by manufacturing process residues or external environmental pollution. Pollution was common in various types of paper products. Although some traditional PFASs were under control, new PFASs and their precursors were still being detected, and the degree of pollution in different countries and regions was affected by regulatory efforts. In terms of dietary exposure, PFASs in food contact paper could migrate to food and enter the human body through dietary intake. Migration was affected by temperature, time, and food properties. The risks of using fast food paper at high temperatures should be closely monitored.Many countries and regions have implemented controls on PFASs, with different limit requirements. China also prohibited the production, processing, and use of some PFASs and adopted forward inventory management. Detection technologies included quantitative analysis of targeted PFASs, fluorine content screening, and non-targeted analysis of unknown PFASs. In the future, research on PFASs in food contact paper should focus on comprehensive assessment, combining multiple analytical methods, and tracing the source, distribution and toxicity hazards of unknown PFASs to improve regulatory regulations.

Keywords：food contact paper; per- and polyfluoroalkyl substances; toxicity hazard; dietary exposure; detection technology

doi：10.12301/spxb202400451

文章编号：2095-6002(2024)06-0025-10

引用格式：林勤保,杨青华,赵丹,等.食品接触用纸中全氟或多氟烷基化合物的来源、限量及检测技术研究进展[J]. 食品科学技术学报,2024,42(6):25-34.

LIN Qinbao,YANG Qinghua,ZHAO Dan, et al. Research progress on source, limitation and detection technology of per- and polyfluoroalkyl substances in food contact paper[J]. Journal of Food Science and Technology, 2024,42(6):25-34.

中图分类号：TS201.2

文献标志码：A

收稿日期：2024-07-09

基金项目：珠海市产学研协同创新计划项目(2220004003084)。

Foundation： Zhuhai Industry-University-Research Cooperation and Innovation Projects (2220004003084).

第一作者：林勤保,男,研究员,博士,主要从事食品包装安全方面的研究。

(责任编辑：李 宁)