المعرفة

الفاعلات بالسطح الفلورية

"PFAS" تحوّل إلى هنا. لمطالعة استخدامات أخرى، انظر PFAS (توضيح).

الفاعلات بالسطح الفلورية (إنگليزية: Per- and polyfluoroalkyl substances، اختصاراً PFASs)، هي مركبات كيميائية فلورية عضوية لديها ذرات فلور متعددة مرتبطة بسلسلة ألكيل. بحسب تعريف مبكر من عام 2011، يلزم أن تحتوي هذه المواد على جزء فاعل بالسطح فلوري واحد على الأقل، –CnF2n+1–.[1][2] بدءاً من عام 2021، مددت منظمة التعاون والتنمية الاقتصادية مصطلحها، حيث أعلنت أن "الفاعلات بالسطح الفلورية معرفة بأنها مواد مفلورة تحتي على ميثيل مفلور كامل واحد على الأقل أو ذرة كربون المثيلين (دون أي ذرة H/Cl/Br/I مرتبطة)، أي، مع استثناءات قليلة ملحوظة، أي مادة كيميائية تحتوي على الأقل على مجموعة ميثيل مشبعة بالفلور (–CF3) أو مجموعة ميثلين مشبعة بالفلور، تعتبر من الفاعلات بالسطح الفلورية."[3][4]

بحسب منظمة التعاون والتنمية الاقتصادية، هناك على الأقل 4.730 مادة مختلفة مصنفة ضمن الفاعلات بالسطح الفلورية، والتي تحتوي على ثلاث ذرات كربون مفلورة على الأقل.[5] قاعدة بيانات السمية بحسب الوكالة الأمريكية لحماية البيئة، DSSTox، تدرج 14.735 مركب كيميائي مختلف من الفاعلات بالسطح الفلورية.[6] وتدرج پب كم 6 مليون مركب كيميائي.[7]


التركيب الهيكلي للفاعلات بالسطح الفلورية.
نموذج ملء الفراغ للفاعلات بالسطح الفلورية.


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الفاعلات السطحية الفلورية

 
Fluorine-containing durable water repellent makes a fabric water-resistant.

Fluorosurfactants are surfactants containing fluorocarbon chains such as those in PFASs. They can reduce the surface tension of water below what is attainable by using hydrocarbon surfactants.[8] This ability is due to the hydrophobic nature of fluorocarbons, so fluorosurfactants tend to concentrate at the liquid-air interface.[9] Fluorocarbons are lipophobic, as well as hydrophobic, allowing them to repel both oil and water. This lipophobicity results from the lack of attractive London dispersion forces in fluorocarbons compared to hydrocarbons, a consequence of fluorine's large electronegativity and small bond length, which reduce the polarizability of the surfactants' fluorinated molecular surface. Fluorosurfactants are more stable and fit for harsher conditions than hydrocarbon surfactants because of the stability of the carbon–fluorine bond. Perfluorinated surfactants persist in the environment for this same reason.[10]


الدور الاقتصادي

PFASs play a key economic role for companies such as DuPont, 3M, and W. L. Gore & Associates because they are used in emulsion polymerization to produce fluoropolymers. They have two main markets: a $1 billion annual market for use in stain repellents, and a $100 million annual market for use in polishes, paints, and coatings.[11]

مخاطر صحية وبيئية

المخاطر الصحية البشرية المرتبطة

عند طرحهم في الأربعينيات، كانت مواد الفاعلات بالسطح الفلورية تعتبر مواد خاملة.[12][13] في الواقع، كشفت الدراسات المهنية المبكرة عن مستويات مرتفعة من المواد الكيميائية الفلورية، بما في ذلك حمض پيرفلوروأوكتان السلفونيك (سلفونات مشبعة بالفلور أوكتين) وحمض الپيرفلوروكتانويك (PFOA، C8)، في دماء العاملين في المجال الصناعي المتعرضين لتلك المواد، لكن لم تذكر أي آثار صحية سيئة.[14][15] كانت هذه النتائج متسقة مع تركيزات مصل PFOS وPFOA في دماء 3 ملايين من عمال مصنع 3M، تتراوح من 0.04 إلى 10.06 جزء في المليون و0.01 إلى 12.70 جزء في المليون على التوالي، أقل بكثير من المستويات السامة والمسرطنة المذكورة في الدراسات على الحيوانات.[12]

 
آثار التعرض للفاعلات بالسطح الفلورية على صحة البشر.[16][17][18][19][20][21]

المواد الكيمائية المسببة لاضطراب الهرومونات، ومن بينها الفاعلات بالسطح الفلورية، مرتبطة بالتراجع السريع في خصوبة البشر.[22] في تحليل شمولي عن علاقة الفاعلات بالسطح الفلورية والواصمات الحيوية السريرية البشرية بالنسبة لإصابة الكبد، نظر الباحثون في كل من تأثيرات الفاعلات بالسطح الفلورية على المؤشرات الحيوية للكبد والبيانات النسيجية من الدراسات التجريبية على القوارض وخلصوا إلى وجود أدلة تظهر أن PFOA، حمض پيرفلوروهكسان السلفونيك (PFHxS)، وحمض الپيرفلورونونانيك (PFNA) هي مواد سامة على الكبد لدى البشر.[23]

العديد من الدراسات الوبائية الشاملة التي تربط بين الآثار الضارة على صحة الإنسان والفاعلات بالسطح الفلورية، وخاصة PFOA، تأتي من لجنة العلوم C8.[24] تشكلت هذه اللجنة كجزء من دعوى طارئة جماعية رفعتها المجتمعات في وادي نهر أوهايو ضد شركة دوپونت ردًا على مدافن النفايات ومياه الصرف الصحي لمواد محملة بالفاعلات بالسطح الفلورية من مصنع وست ڤرجينيا واشنطن للأشغال التابع لشركة دوپونت .[24] قامت اللجنة بقياس تركيزات مصل PFOA (الذي يُعرف أيضاً باسم C8) لـ69.000 فرد من المصنع وكان متوسط التركيزات 83.0 ن.گ/مل، مقارنة بـ 4 ن.گ/مل بين الشعب الأمريكي.[25] أفادت هذه اللجنة بوجود روابط محتملة بين ارتفاع مستويات[vague] PFOA في الدم وفرط كولسترول الدم، التهاب القولون التقرحي، أمراض الغدة الدرقية، سرطان الخصية، سرطان الكلى وكذلك فرط ضغط الدم أثناء الحمل وتسمم الحمل.[26][27][28][29][30]

صحة المرأة

 
ملابس داخلية للدورة الشهرية من إنتاج شركة ثينكس.

في يناير 2023، نجحت شركة ثينكس للملابس الداخلية بتسوية دعوى قضائية تزعم أن منتجاتها تحتوي على مركبات كيميائية ضارة، مما أثار المزيد من الأسئلة حول سلامة منتجات الدورة الشهرية بشكل عام. الدعوى التي رُفعت منذ عام 2020، تدعي أن منتجات ثينكس تحتوي على مواد كيميائية ضارة، ومن ضمن هذه المواد الفاعلات بالسطح الفلورية، والمواد الكيميائية الباقية للأبد.

تصمم الشركة ملابس داخلية تستخدم في فترة الحيض لتعمل مثل الفوط الصحية التقليدية، لامتصاص الدم، لكنها على عكس الفوط التي تستخدم لمرة واحدة، يمكن غسلها وإعادة استخدامها مرة أخرى. تم الكشف عن وجود الفاعلات بالسطح الفلورية في منتجات ثينكس لأول مرة في يناير 2020، عندما نشرت مجلة سييرا تحقيقا، بالشراكة مع باحث في جامعة نوتردام، وجد هذه المواد الكيميائية في منطقة المنفرج (الجزء السفلي من الحوض) في إحدى القطع الداخلية من إنتاج ثينكس. وتضمنت ثلاث دعاوى قضائية مختلفة على الأقل مرفوعة ضد ثينكس أدلة إضافية من مختبرين تابعين لجهات خارجية على وجود الفاعلات بالسطح الفلورية وسمومأخرى في الملابس الداخلية.

في النهاية، دُمجت عدد من الدعاوى القضائية في قضية واحدة جماعية وتوصلت الشركة إلى تسوية في نهاية عام 2022. في يناير 2023، أصبح بإمكان المستهلكين البدء في التقدم بطلب لاسترداد ما يصل إلى ثلاثة أزواج من الملابس الداخلية ثينكس، مقابل 7 دولارات لكل زوج للأشخاص الذين لا يزالون يحتفظون بإيصالات الشراء و3.50 دولارًا لأولئك الذين ليس لديهم إيصالات. في بيان أرسلته ثينكس لنيويورك تايمز في نهاية يناير 2023، كتبت: "إن الفاعلات بالسطح الفلورية لم تكن أبدًا جزءًا من تصميم منتجاتنا" وأن العلامة التجارية ستتخذ، من الآن فصاعدًا، تدابير لضمان عدم "إضافة المواد الكيميائية إلى منتجاتنا". وكتبت أن التسوية "ليست اعترافاً بالذنب أو الخطأ".

ومع ذلك، فإن جوهر هذه الدعاوى القضائية هو أنه بينما توجد الفاعلات بالسطح الفلورية والسموم البيئية الأخرى في مجموعة واسعة من المنتجات الاستهلاكية، ضللت ثينكس المستهلكين، وقامت بتسويق نفسها كبديل "عضوي ومستدام وغير سام" لمنتجات الدورة الشهرية التقليدية ذات الاستخدام الواحد، بما في ذلك الفوط والسدادات القطنية. جادل المحامون بأن الخداع "يجعل ملابس ثينكس الداخلية عديمة القيمة"، لا سيما في الوقت الذي يسعى فيه عدد متزايد من النساء في فترة الحيض - وخاصة مستهلكي الجيل Z - بشكل استباقي إلى الحصول على منتجات أكثر أمانًا وصديقة للبيئة.[31]

بالنسبة للآباء، أثارت أخبار التسوية مخاوف بشأن مدى أمان منتجات فترة الحيض لبناتهم. قال الدكتور شروثي ماهالينگاياه، باحث الصحة البيئية في جامعة هارڤرد: "لقد اشتريت أيضًا زوجًا من الملابس الداخلية لفترة قصيرة لابنتي". وعلقت كلية تشان للصحة العامة التي تركز على تأثير السموم البيئية على الصحة الإنجابية للمرأة: "البحث عن منتجات آمنة كانت ذات علامة تجارية عضوية وطبيعية أثرت على خيارات الشراء لدينا". وأضافت: "إذا كنت، بصفتي شخصًا ذا خبرة، ما زلت أواجه صعوبات في تحديد ما هو آمن لأطفالي، فلا أظن أنه من الأسهل على أي شخص آخر".

غالبًا ما يطلق على الفاعلات بالسطح الفلورية اسم "المواد الكيميائية الباقية إلى الأبد" لأنها غير قابلة للتدمير عمليًا. منذ أواخر الثلاثينيات، استخدمت هذه المواد الكيميائية في جميع أنواع المنتجات الاستهلاكية تقريبًا، بما في ذلك أواني الطهي والشامبو ومنتجات التنظيف ومستحضرات التجميل، لجعل المنتجات مقاومة للماء أو الزيت أو الحرارة. يمكن أيضًا استخدامها لجعل الملابس مقاومة للماء - وهو ما تدعي الدعوى القضائية أن الملابس الداخلية من ثينكس تمتص دم الدورة الشهرية ولا تزال تشعر بالجفاف.

قال الدكتور ماهالينگاياه إن الفاعلات بالسطح الفلورية قد تلوث أي شيء تلمسه (بما في ذلك الطعام المغلف في عبوات تحتوي على هذه المواد) ولا تتحلل بشكل طبيعي، ولا تستطيع أجسامنا استقلابها. وبدلاً من ذلك، تتراكم في أجسادنا وفي البيئة، وتلوث التربة والهواء والماء.

نظرًا لأن هذه المركبات الكيميائية لا مفر منها، فإن معظم الناس في الولايات المتحدة "لديهم الفاعلات بالسطح الفلورية في دمائهم"، وفقًا لوكالة تسجيل المواد السامة والأمراض.

يشكل التعرض للفاعلات بالسطح الفلورية وتراكمها في الجسم العديد من المخاطر الصحية طويلة الأجل. عام 2017، صنفت الوكالة الدولية لأبحاث السرطان بعض الفاعلات بالسطح الفلورية كمواد مسرطنة محتملة. كما تعطل الفاعلات بالسطح الفلورية الوظائف الهرمونية، وقد أشارت بعض الأبحاث إلى أنها مرتبطة بتقدم عمر المبيض المتسارع، وعدم انتظام الدورة الشهرية، واضطرابات المبيض مثل متلازمة تكيس المبايض.

بالنسبة الحوامل، ارتبطت الفاعلات بالسطح الفلورية بزيادة خطر الإصابة بارتفاع ضغط الدم، أو تسمم الحمل، وتشير بعض الأبحاث إلى أن الأطفال الذين يتعرضون في الرحم يواجهون خطرًا متزايدًا لانخفاض الوزن عند الولادة. ومع ذلك، تحذر مراكز السيطرة على الأمراض والوقاية منها من أن الآثار الصحية للفاعلات بالسطح الفلورية لا تزال "غير مؤكدة" لأن العديد من الدراسات أجريت على حيوانات المختبر التي تتعرض لمستويات PFA "أعلى من الجرعات التي يتعرض لها الأشخاص من التعرض البيئي.

قالت الدكتورة ماريانثي آنا كيومورزوگلو، مهندسة البيئة وعالمة الأوبئة في كلية كولومبيا ميلمان للصحة العامة، إن أحد الاهتمامات الرئيسية بالفاعلات بالسطح الفلورية في منتجات الفترة هو أن منطقة المهبل حساسة للغاية. في الواقع، أظهرت الدراسات أن القناة المهبلية يمكن أن تكون قناة فعالة لتوصيل أدوية معينة إلى مجرى الدم بسبب طبيعتها شديدة الامتصاص.

يقول الدكتور ماهالنگاياه، إن الخبراء قلقون أيضًا بشأن تأثيرات الفاعلات بالسطح الفلورية خلال المراحل التي يكون فيها الجسم ضعيفًا بشكل خاص، مثل عندما تكون المرأة في فترة الدورة الشهرية أو تكون حاملاً أو في مرحلة ما قبل انقطاع الطمث. خلال هذه الأوقات، يخضع الجسم والدماغ لتحولات كبيرة، مما يجعلهما أكثر حساسية تجاه اضطرابات الغدد الصماء. ما هو غير واضح عندما يتعلق الأمر بمنتجات الحيط، ومع ذلك، هو ما إذا كانت الفاعلات بالسطح الفلورية في هذه المنتجات قادرة على التسرب إلى مجرى الدم بتركيزات أعلى مما تفعله عبر المنتجات الأخرى، مثل تغليف المواد الغذائية أو الشامبو. قالة الدكتورة كيومورزوگلو: "الإجابة المختصرة هي أننا لا نعرف لأن هذا موضوع غير مدروس".

من الصعب معرفة ذلك. قالت الدكتورة شارا فوسترال، أستاذة التاريخ في جامعة بوردو التي درست السياسات والتصميم وعمليات الموافقة وراء منتجات الدورة الشهرية، إنه كان هناك "تاريخ طويل من الافتقار إلى الرقابة" عندما يتعلق الأمر بمنتجات الدورة الشهرية. وأضافت: "بشكل عام، لم يتم اختبارها وفهمها بشكل كامل".

على الرغم من أن أكواب الحيض والسدادات القطنية والفوط تعتبر أجهزة طبية، إلا أن إدارة الغذاء والدواء تصنفها على أنها منخفضة أو متوسطة عالية الخطورة. أكدت شركة ثينك أنها سجلت ملابسها الداخلية كجهاز طبي. بسبب التصنيف، لا تخضع هذه المنتجات لاختبارات صارمة، ولا يحتاج المصنعون إلى تصنيف جميع المواد المستخدمة فيها.

قال الدكتور كيومورزوگلو إنه من غير الواضح إذن ما هي منتجات فترة الحيض التي تحتوي على الفاعلات بالسطح الفلورية أو سموم بيئية أخرى، بالإضافة إلى تركيز السموم في تلك المنتجات ومقدار امتصاصها من قبل الجسم. وفي الوقت نفسه، وجدت الدراسات التي تمت مراجعتها من قبل الأقران لهذه المنتجات نتائج غير متسقة. فحص تحليل حديث أجراه الدكتور كيومورزوگلو والعديد من الزملاء ما يقرب من عشرين دراسة. وجدت بعض الدراسات كميات كبيرة من مجموعة من السموم في منتجات الفترة ، بينما وجدت دراسات أخرى كميات ضئيلة فقط تمثل "خطرًا منخفضًا على الصحة"، مما دفع المؤلفين إلى استنتاج أن هناك حاجة إلى مزيد من البحث.

عندما يتعلق الأمر بالملابس الداخلية الخاصة بلدورة الشهرية، يقترح بعض الخبراء أن غسل هذه الملابس مرة بعد مرة قد يعمل على التخلصمن الفاعلات بالسطح الفلورية، لكن لا يوجد بحث علمي يؤكد ذلك. ولم تنظر الدراسات على وجه التحديد في ما إذا كان الجسم يمتص الفاعلات بالسطح الفلورية الموجودة في الملابس الداخلية الخاصة بالحيض، حتى أن دعوى ثينكس القضائية كانت تركز على تسويقها وليس حول أي مشكلات صحية قد يواجهها المستهلكون. ومع ذلك، لم تصمم جميع الملابس الداخلية بنفس الطريقة. حدد التحقيق الأصلي الذي أجرته مجلة سييرا ومختبرو المنتجات الآخرون بعض العلامات التجارية التي يزعمون أنها خالية من السموم.

يقترح الخبراء أيضًا استخدام أكواب الدورة الشهرية المصنوعة من السيليكون الطبي، والتي قال الدكتور ماهالينگايا إنها من المحتمل أن تكون "خاملة". وأضاف: "آمل أن نرى ابتكارات وأنواع جديدة من المنتجات القائمة على السيليكون".


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تواجدها في مياه الأمطار

In 2022 it was found that levels of at least four perfluoroalkyl acids (PFAAs) in rainwater worldwide ubiquitously, and often greatly, exceeded the EPA's lifetime drinking water health advisories as well as comparable Danish, Dutch, and European Union safety standards, leading researchers to conclude that "the global spread of these four PFAAs in the atmosphere has led to the planetary boundary for chemical pollution being exceeded".[32] There are some moves to restrict and replace their use.[33]

تقدير التكاليف المعاصرة

انظر أيضاً: العوامل الخارجية

In a report by the Nordic Council of Ministers the total annual health-related costs associated with human exposure to PFASs were estimated to be at least €52-€84 billion in the European Economic Area (EEA) countries.[34] For the United States, estimated PFAS-attributable disease costs amount to 6–62 billion US$.[35] Aggregated annual costs covering environmental screening, monitoring where contamination is found, water treatment, soil remediation and health assessment total €821 million-€170 billion in the EEA plus Switzerland.[34]

الآليات المقترحة للنتائج الصحية الضارة المرتبطة

فرط كولسترول الدم

Animal studies in the 1990s and early 2000s primarily aimed to investigate the effect of two widely used long-chain PFASs, perfluorooctanoic acid (PFOA, C8) and perfluorooctane sulphonic acid (PFOS, C8), on peroxisome proliferation in rat livers.[36] These studies determined that PFOA and PFOS acted as peroxisome proliferator-activated receptor (PPAR) agonists, increasing lipid metabolism.[36] A paradoxical response is observed in humans where elevated PFOS levels were significantly associated with[vague] elevated total cholesterol and LDL cholesterol, highlighting significantly reduced PPAR expression and alluding to PPAR independent pathways predominating over lipid metabolism in humans compared to rodents.[37]

التهاب القولون التقرحي

PFOA and PFOS have been shown to significantly alter immune and inflammatory responses in human and animal species. In particular, IgA, IgE (in females only) and C-reactive protein have been shown to decrease whereas antinuclear antibodies increase as PFOA serum concentrations increase.[38] These cytokine variations allude to immune response aberrations resulting in autoimmunity. One proposed mechanism is a shift towards anti-inflammatory M2 macrophages and/or T-helper (TH2) response in intestinal epithelial tissue which allows sulfate-reducing bacteria to flourish. Elevated levels of hydrogen sulfide result which reduce beta-oxidation and thus nutrient production leading to a breakdown of the colonic epithelial barrier.[39]

أمراض الغدة الدرقية

Hypothyroidism is the most common thyroid abnormality associated with[vague] PFAS exposure.[40] PFASs have been shown to decrease thyroid peroxidase, resulting in decreased production and activation of thyroid hormones in vivo.[41] Other proposed mechanisms include alterations in thyroid hormone signaling, metabolism and excretion as well as function of nuclear hormone receptor.[40]

السرطان

Rat studies investigating the carcinogenicity of PFASs reported significant correlation with liver adenomas, Leydig cell tumors of the testis and pancreatic acinar cell tumors and dietary PFOA consumption.[41] The C8 Science Panel investigated the potential relationship between PFAS exposure and these three cancer types as well as 18 other cancer types in their epidemiological studies. Contrary to the animal studies, the C8 studies did not find a probable link[vague] between elevated C8 exposure and liver adenomas or pancreatic acinar cell tumors; however, a probable link[vague] was found with regards to testis and kidney cancer.[42] Two mechanisms have been proposed by which PFOA could cause Leydig cell tumors. Both mechanisms start by proposing that PROA exposure results in increased PPAR alpha activation in the liver which increases hepatic aromatase concentration and subsequent serum estrogen levels. The mechanisms now diverge, with one pathway suggesting elevated estradiol levels increase Tissue Growth Factor alpha (TGF alpha) which prompts Leydig cell proliferation. The other pathway suggests that aromatization of testosterone to estradiol reduces serum testosterone levels resulting in increased release of luteinizing hormone (LH) from the pituitary gland which directly results in Leydig Cell tumorgenesis.[43] A mechanism has not yet been proposed to explain how kidney cancer could be caused by C8 exposure as no in vivo animal studies have been able to model this epidemiological outcome.[44]

ارتفاع ضغط الدم الناجم عن الحمل وتسمم الحمل

Pregnancy-induced hypertension is diagnosed when maternal systolic blood pressure exceeds 140 mmHg or diastolic blood pressure exceeds 90mmHg after 20 weeks gestation.[45] Diagnostic criteria are the same for pre-eclampsia as pregnancy-induced hypertension; however, it also confers proteinuria. Mechanisms by which pregnancy-induced hypertension and preeclampsia could be caused by PFAS exposure have remained elusive and are largely speculative to date. One proposed mechanism highlights alterations in immune function leading to disruption of placentation, specifically as it pertains to natural killer (NK) cell infiltration of the placenta to facilitate trophoblastic integration with placental blood supply.[46] Another mechanism refers to agonism of PPARs contributing to alterations in cholesterol, triglyceride and uric acid levels which may lead to vascular inflammation and elevated blood pressure.[46]

Other adverse health outcomes that have been attributed to elevated PFAS exposure but were not found to be probable links[vague] in the C8 studies are decreased antibody response to vaccines, asthma, decreased mammary gland development, low birth weight (-0.7oz per 1 ng/mL increase in blood PFOA or PFOS level), decreased bone mineral density and neurodevelopmental abnormalities.[47][48][49]

المواد الكيميائية الباقية إلى الأبد

Fluorosurfactants such as PFOS, PFOA, and PFNA have caught the attention of regulatory agencies because of their persistence, toxicity, and widespread occurrence in the blood of general populations[50][51] and wildlife. In 2009, PFOS, its salts and perfluorooctanesulfonyl fluoride were listed as persistent organic pollutants under the Stockholm Convention, due to their ubiquitous, persistent, bioaccumulative, and toxic nature.[52][53] PFAS chemicals were dubbed the "Forever Chemicals" following a 2018 op-ed in the Washington Post.[54] The nickname was derived by combining the two dominant attributes of this class of chemicals: 1) PFAS chemicals are characterized by a carbon-fluorine (C-F) backbone (the "F-C" in "Forever Chemicals"); and 2) the carbon fluorine bond is one of the strongest bonds in organic chemistry, which gives these chemicals an extremely long environmental half-life (the "Forever" in "Forever Chemicals"). The Forever Chemicals name is now commonly used in media outlets in addition to the more technical name of per- and polyfluorinated alkyl substances, or PFASs.[55][56][57][58] Their production has been regulated or phased out by manufacturers, such as 3M, DuPont, Daikin, and Miteni in the US, Japan, and Europe. In 2006 3M replaced PFOS and PFOA with short-chain PFASs,[11] such as perfluorohexanoic acid (PFHxA) and perfluorobutanesulfonic acid (PFBS). Shorter fluorosurfactants may be less prone to accumulating in mammals;[11] there is still concern that they may be harmful to both humans,[59][60][61] and the environment.[62] A majority of PFASs are either not covered by European legislation or are excluded from registration obligations under the EU REACH chemical regulation.[63] Several PFASs have been detected in drinking water,[64] municipal wastewater[65] and landfill leachates,[66] worldwide.

It had been thought that perfluoroalkyl acids (PFAAs) would eventually end up in the oceans, where they would be diluted over decades, but a field study published in 2021 by researchers at Stockholm University found that they are significantly transferred from water to air when waves break on land, and are a significant source of air pollution, and eventually get into the rain. The researchers concluded that pollution "may impact large areas of inland Europe and other continents, in addition to coastal areas".[67][68]


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التراكم الأحيائي والتضخم الأحيائي

 
Bioaccumulation of PFAS: PFASs from sediments and water can accumulate in marine organisms. Animals higher up the food chain accumulate more PFAS because they absorb PFAS in prey they consume.

Bioaccumulation is the process by which PFASs are transferred into the tissue of any exposed organisms where PFASs accumulate over time since organisms lack natural excretion mechanisms. PFASs can accumulate in marine species by a variety of pathways. They can be absorbed from the environment, such as contaminated sediments or PFASs dissolved in water. PFASs can partition into the organs and tissues of marine organisms from these environmental compartments. They have been shown to bind to blood proteins and accumulate in the livers of marine animals.[69] Another pathway for bioaccumulation is predation. As larger marine animals feed on smaller organisms that have been exposed to PFASs, the larger animals absorb the PFASs contained in their prey.

 
Biomagnification is the build up of toxins in a food chain. As the trophic level increases in a food chain, the amount of toxic build up increases. The x's represent the amount of toxic build up accumulating as the trophic level increases. Toxins build up in organism's fat and tissue. Predators accumulate higher toxins than prey as a result of bioaccumulation.

Biomagnification is the process by which the amount of PFAS contamination increases with increasing trophic level, due to predation by the species higher in the food web. Top predators have higher levels of PFASs than species lower down the food chain. Seabirds that feed on fish have among the highest levels of PFAS contamination.[69] Perfluorosulfonic acids, which have a sulfonic acid functional group attached to the fluorinated "tail", have a greater tendency to bioaccumulate than perfluorocarboxylic acids, which contain a carboxylic acid function group. Longer chain PFAS compounds, which have 6, 7, or more fluorinated carbons, bioaccumulate in greater quantities than shorter chain PFAS compounds. The concentration of PFOS, a long chain sulfonic acid, was found at the highest concentrations relative to other PFASs measured in fish and birds in Northern seas such as the Barents Sea and the Canadian Arctic.[70]

Bioaccumulation and biomagnification of PFASs in marine species throughout the food web, particularly frequently consumed fish and shellfish, can have important impacts on human populations.[71] PFASs have been frequently documented in both fish and shellfish that are commonly consumed by human populations.[72] This poses health risks to humans and studies on the bioaccumulation in certain species are important to determine daily tolerable limits for human consumption, and where those limits may be exceeded causing potential health risks.[73] This has particular implications for populations that consume larger numbers of wild fish and shellfish species.[72] In addition to health risks, populations may be impacted by advisories, limits of closures of fishing for certain species that are put in place to help mitigate health risks from potential consumption of species with higher levels of accumulated PFASs, but result in a lost of food sources and important subsistence species depended on by local communities. There is much research being done in this area, including into spatial patterns of PFAS bioaccumulation in fish and crustaceans[74] but more research is also needed. There is a need for more research on membrane transport mechanisms, which transfer PFAS into marine organisms, and the biological behavior of shorter chain PFASs.[75]

أستراليا

كندا

المملكة المتحدة

إيطاليا

الولايات المتحدة

 
قد يحتوي أحمر الشفاة السائل على الفاعلات بالسطح الفلورية.



الدعاوى القضائية الجماعية

In February 2017, DuPont and Chemours (a DuPont spin-off) agreed to pay $671 million to settle lawsuits arising from 3,550 personal injury claims related to releasing of PFASs from their Parkersburg, West Virginia plant, into the drinking water of several thousand residents.[76] This was after a court-created independent scientific panel, the "C8 Science Panel", found a "probable link" between C8 exposure and six illnesses: kidney and testicular cancer, ulcerative colitis, thyroid disease, pregnancy-induced hypertension and high cholesterol.[24][77]

In October 2018, a class action suit was filed by an Ohio firefighter against several producers of fluorosurfactants, including the 3M and DuPont corporations, on behalf of all US residents who may have adverse health effects from exposure to PFASs.[78]

This story is told in the film Dark Waters, released in November 2019, produced by the actor Mark Ruffalo and directed by Todd Haynes.[79]

تكتم الشركات والحكومات الفدرالية على المعلومات

Starting in the 1970s, 3M scientists learned that PFOS and PFOA were toxic to humans, documenting damage to the human immune system. Also in the 1970s, 3M scientists found that these substances accumulate over time in the human body. However, 3M suppressed revelation of these facts to the public or to regulators.[80]

In 2018 White House staff and EPA pressured the U.S. Agency for Toxic Substances and Disease Registry to suppress a study that showed PFASs to be even more dangerous than previously thought.[81][82]

تلوث المياه من القواعد العسكرية الأمريكية

The water in and around at least 126 U.S. military bases has been contaminated by high levels of PFASs because of their use of firefighting foams since the 1970s, according to a study by the U.S. Department of Defense. Of these, 90 bases reported PFAS contamination that had spread to drinking water or groundwater off the base.[83][84] A 2022 Pentagon report acknowledged that approximately 175,000 U.S. military personnel at two dozen American military facilities drank water contaminated by higher PFAS levels than the U.S. Environmental Protection Agency limit. However, according to an analysis of the Pentagon report by the non-partisan Environmental Working Group, the Pentagon report downplayed the number of people exposed to PFAS, which was much higher, probably in excess of 640,000 at 116 military facilities, than the number advanced by the Pentagon report. The EWG found that the Pentagon also omitted from its report some types of diseases that are likely to be caused by EWG exposure, omitting testicular cancer, kidney disease, and fetal abnormalities.[85]

التعرض المهني

Occupational exposure to PFASs occurs in numerous industries due to the widespread use of PFASs in products and as an element of industrial process streams.[17] PFASs are used in more than 200 different ways in industries as diverse as electronics and equipment manufacturing, plastic and rubber production, food and textile production, and building and construction.[86] Occupational exposure to PFASs can occur at fluorochemical facilities that produce PFASs and other manufacturing facilities that use PFASs for industrial processing like the chrome plating industry.[17] Workers who handle PFAS-containing products can also be exposed during their work. Examples include people who install PFAS-containing carpets and leather furniture with PFAS coatings, professional ski-waxers using PFAS-based waxes, and fire-fighters who use PFAS-containing foam and wear flame-resistant protective gear impregnated with PFASs.[17][87][88][89][90]

People who are exposed to PFASs through their jobs typically have higher levels of PFASs in their blood than the general population.[17][88][89][91][92] Additionally, while the general population is exposed to PFASs through ingested food and water, occupational exposure includes both accidental ingestion and inhalation exposure in settings where a PFAS becomes volatilized.[93] There has been increased attention to the health risks associated with exposure to PFASs, which can affect the immune system, increase cholesterol, and increase the risk of cancer.[47] The severity of PFAS-associated health effects can vary based on the length of exposure, level of exposure, and health status.[17] In 2009, under decision SC-4/17, perfluorooctane sulfonic acid, its salts and perfluorooctane sulfonyl fluoride were listed in Annex B of the 2009 Stockholm Convention on Persistent Organic Pollutants, dictating acceptable purposes and specific exemptions to the chemical usage. Among these exemptions are numerous uses in manufacturing as well as firefighting foams.

تقنيو شمع التزلج المحترفون

Professional ski wax technicians are disproportionately exposed to PFASs from the glide wax used to coat the bottom of skis to reduce the friction between the skis and snow. During this process, the wax is heated to 130-220 °C, which releases fumes and airborne fluorinated compounds. Exposure to aerosolized PFASs is associated with alveolic edema, polymer fume fever, severe dyspnea, decreased pulmonary function, and respiratory distress syndrome in those chronically exposed.[88] In a 2010 study, blood serum levels of PFOA were significantly higher in ski wax technicians compared to levels of the general Swedish population. Serum levels of PFOA in ski wax technicians were positively correlated with years spent working, suggesting bioaccumulation of PFOA over time.[88]

عمال التصنيع

People who work at fluorochemical production plants and in manufacturing industries that use PFASs in the industrial process can be exposed to PFASs in the workplace. Much of what we know about PFASs exposure and health effects began with medical surveillance studies of workers exposed to PFASs at fluorochemical production facilities. These studies began in the 1940s and were conducted primarily at U.S. and European manufacturing sites. Between the 1940s and 2000s, thousands of workers exposed to PFASs participated in research studies that advanced scientific understanding of exposure pathways, toxicokinetic properties, and adverse health effects associated with exposure.[14][94][95][15][96][97][98][99][100][101][102][103][104]

The first research study to report elevated organic fluorine levels in the blood of fluorochemical workers was published in 1980.[14] This study established inhalation as a potential route of occupational PFAS exposure by reporting measurable levels of organic fluorine in air samples at the facility.[14] Workers at fluorochemical production facilities have higher levels of PFOA and PFOS in their blood than the general population. Serum PFOA levels in fluorochemical workers are generally below 20,000 ng/mL but have been reported as high as 100,000 ng/mL whereas the mean PFOA concentration among non-occupationally exposed cohorts in the same time frame was 4.9 ng/mL.[101][15][105][106][107][108][109][110][111][112] Among fluorochemical workers, those with direct contact with PFASs have higher PFAS concentrations in their blood than those with intermittent contact and those with no direct PFAS contact.[14][94][101] Further, blood PFAS levels decline when direct contact ceases.[101][96][98] Levels of PFOA and PFOS have declined in US and European fluorochemical workers due to improved facilities, increased usage of personal protective equipment, and the phase out of these chemicals from production.[94][102][104] However, occupational exposure to PFASs in manufacturing continues to be an active area of study in China with numerous investigations linking worker exposure to various PFASs.[113][114][115][116][117]

إطفاء الحرائق

 
رجال المطافي يستخدمون رغوة التشكيل الغشائية (AFFF).

PFASs are commonly used in Class B firefighting foams due to their hydrophobic and lipophobic properties as well as the stability of the chemicals when exposed to high heat.[118] Due to firefighters' potential for exposure to PFASs through these aqueous film forming foams (AFFF), studies raise concerns that firefighters are especially prone to high concentrations of serum PFASs.

Research into occupational exposure for firefighters is emergent, though frequently limited by underpowered study designs. A 2011 cross-sectional analysis of the C8 Health Studies found higher levels of PFHxS in firefighters compared to the sample group of the region, with other PFASs at elevated levels, without reaching statistical significance.[119] A 2014 study in Finland studying eight firefighters over three training sessions observed select PFASs (PFHxS and PFNA) increase in blood samples following each training event.[118] Due to this small sample size, a test of significance was not conducted. A 2015 cross-sectional study conducted in Australia found  that accumulation of PFOS and PFHxS was positively associated with years of occupational AFFF exposure through firefighting.[89]

Due to their use in training and testing, recent studies indicate occupational risk for military members and firefighters, as higher levels of PFASs in exposure were indicated in military members and firefighters when compared to the general population.[120] Further, exposure to PFASs is prevalent among firefighters not only due to its use in emergencies but because it is also used in personal protective equipment. In support of these findings, states like Washington and Colorado have moved to restrict and penalize the use of Class B firefighting foam which contains PFASs for firefighter training and testing.[121][122]

التعرض لهجمات إرهابية بعد مركز التجارة العالمي

The September 11, 2001 collapse of the World Trade Center buildings in New York City resulted in the release of chemicals from the destruction of construction and electrical material and long-term chemical fires. This collapse caused the release of several toxic chemicals, including fluorinated surfactants used as soil- and stain-resistant coatings on various materials.[123] First responders to this incident were exposed to PFOA, PFNA, and PFHxS, through inhalation of dust and smoke released during and after the collapse of the World Trade Center.[123]

Fire responders who were working at or near ground zero were assessed for respiratory and other health effects from exposure to emissions at the World Trade Center. Early clinical testing showed a high prevalence of respiratory health effects. Early symptoms of exposure often presented with persistent coughing and wheezing. PFOA and PFHxS levels were present in both smoke and dust exposure. Yet, first responders with smoke exposures had higher concentrations of PFOA and PFHxS than those with dust exposures.[123]

حلول المعالجة

معالجة المياه

Several technologies are currently available for remediating PFASs in liquids. These technologies can be applied to drinking water supplies, groundwater, industrial wastewater, surface water, and other miscellaneous applications (such as landfill leachate). Influent concentrations of PFASs can vary by orders of magnitude for specific media or applications. These influent values, along with other general water quality parameters (for example, pH) can influence the performance and operating costs of the treatment technologies. The technologies are:

Private and public sector applications of one or more of these methodologies above are being applied to remediation sites throughout the United States and other international locations.[126] Most solutions involve on-site treatment systems, while others are leveraging off-site infrastructure and facilities, such as a centralized waste treatment facility, to treat and dispose of the PFAS pool of compounds.

Most recently, a 2022 study published in the Journal of Environmental Engineering found that a heat-and pressure-based technique known as supercritical water oxidation destroyed 99% of the PFASs present in a water sample. During this process, oxidizing substances are added to PFAS-contaminated water and then the liquid is heated above its critical temperature of 374 degrees Celsius at a pressure of more than 220 bars. The water becomes supercritical (being neither gas nor liquid), and, in this state, water-repellent substances such as PFASs dissolve much more readily.[125]

الحلول النظرية والمبكرة

The Michigan State University-Fraunhofer team has a viable solution to treat PFAS-contaminated wastewater that, in 2018, was reported to be ready for a pilot-scale investigation. The electrochemical oxidation system used boron-doped diamond electrodes, in a process breaking down the contaminants' formidable molecular bonds and cleaning the water while systematically destroying the hazardous compounds.[127]

"EO, or electrochemical oxidation, is a simple, clean, and effective method for destruction of PFASs and other co-contaminants as a complementary procedure to other wastewater treatment processes," said Cory Rusinek, an electrochemist at MSU-Fraunhofer. "If we can remove it from wastewater, we can reduce its occurrence in surface waters."[127]

In September 2019, it was reported Acidimicrobium sp. strain A6 could be a potential remediator of PFAS, including saturated ones such as PFOS.[128] PFAS with unsaturated bonds are easier to break down: the commercial dechlorination culture KB1 (contains Dehalococcoides) is capable of breaking down such substances, but not saturated PFAS. When alternative, easier-to-digest substrates are present, microbes may prefer them over PFAS.[129]

المعالجة الكيميائية

A study published in the journal Science in August 2022 indicated that perfluoroalkyl carboxylic acids (PFCAs) are able to be "mineralized" via heating in a polar aprotic solvent such as dimethyl sulfoxide. The study reported that heating PFCAs in an 8 to 1 mixture of dimethyl sulfoxide and water at 80–120 °C (176–248 °F) in the presence of sodium hydroxide, caused the removal of the carboxylic acid group at the end of the carbon chain, creating a perfluoroanion. The perfluoroanion then "mineralizes" into sodium fluoride and other salts such as sodium trifluoroacetate, formate, carbonate, oxalate and glycolate. The process does not work on perfluorosulfonic acids such as PFOS.[130] A more recent study published in Chemical Science shows breakdown of C-F bonds and their mineralization as YF3 or YF6 clusters.[131] Another study in the Journal of the American Chemical Society described the PFAs breakdown using metal-organic frameworks (MOFs).[132]

مثال على المواد الكيميائية

Some common per- and polyfluoroalkyl substances:[133][134]

Name Abbreviation Structural formula Molecular weight (g/mol) CAS No.
Perfluorobutane sulfonamide H-FBSA C4F9SO2NH2 299.12 30334-69-1
Perfluoropentanesulfonamide PFPSA C5F11SO2NH2 349.12 82765-76-2
Perfluorohexanesulfonamide PFHxSA C6F13SO2NH2 399.13 41997-13-1
Perfluoroheptanesulfonamide PFHpSA C7F15SO2NH2 449.14 82765-77-3
Perfluorooctanesulfonamide PFOSA C8F17SO2NH2 499.14 754-91-6
Perfluorobutanesulfonyl fluoride PFBSF C4F9SO2F 302.09 375-72-4
Perfluorooctanesulfonyl fluoride PFOSF C8F17SO2F 502.12 307-35-7

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المصادر

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