Part 1 Basic Definition
Perfluorinated compounds (PFCs) are a class of organic compounds in which all hydrogen atoms on the carbon chain are replaced by fluorine atoms. Due to its good hydrophobic and oleophobic properties, it is often used as a surfactant in industrial and civil fields such as textiles, papermaking, metal electroplating, paint coatings, food packaging, etc., and is closely related to human production and life. Due to their extremely strong stability, PFCs have been detected in large quantities in environmental media and organisms including water, soil, and atmosphere.
As mentioned in the movie "Black Water", PFOA is associated with six serious diseases, including kidney cancer, testicular cancer, ulcerative colitis, thyroid disease, hypercholesterolemia and pregnancy-induced hypertension. Toxicological studies have shown that PFCs are carcinogenic Sex, hepatotoxicity, neurotoxicity, reproductive toxicity, etc.
Perfluorinated compounds can be divided into ionic PFCs and non-ionic PFCs. Ionic perfluorinated compounds can be divided into perfluoroalkyl sulfonic acids (PFSAs) and perfluorocarboxylates There are two types of perfluoroalkyl carboxylic acids (PFCAs). The two most widely used non-ionic compounds are perfluorooctane sulfonamides (FOSAMs) and fluorotelomer acids (FTAs). Most perfluorochemical products contain 4-14 carbon atoms, of which perfluorooctane (C8) products account for more than 80%. Perfluorooctane sulfonate and its salts (perfluorooctane sulphonate, PFOS) and perfluorooctanoic acid and its salts (perfluorooctanoic acid, PFOA) are typical compounds of PFCs. In addition, PFOS is formed after the enzymatic hydrolysis of PFOSF and is also the final degradation product of PFOS products. PFOA is a by-product of the production of perfluorinated alcohol and is also formed during the production of water repellent and antifouling and aqueous film-forming foam (AFFF). Fluorotelomers in food packaging also degrade PFOA is present. The industrial surfactants used by DuPont to make Teflon in the movie also contain PFOA.
In recent years, PFOA and PFOS, as part of a group of chemicals perfluorinated and polyfluoroalkyl substances (PFAS) or perfluorinated compounds (PFC), have been listed as persistent organic pollutants (POPs) The Stockholm Convention Annex B and the European Chemicals Agency's 9th batch of substances of very high concern (substances of very high concern, SVHC). POPs have four properties: high toxicity, persistence, bioaccumulation, and long-range transport, which obviously means that perfluorinated compounds (PFCs) are widely used due to their unique surface activity and chemical stability In products in the fields of life, industry and scientific research, its properties are stable and can migrate over long distances. It has bioconcentration and biotoxicity, and is a persistent organic pollutant.
In addition, polytetrafluoroethylene (PTFE), another man-made chemical repeatedly mentioned in the movie "Black Water", can be used for a long time at -180 to 260ºC. Teflon is the trade name for this polymer. At present, in addition to PTFE, DuPont also uses trademarks on FEP, PFA, ETFE, AF, NXT, FFR and other resins, but more than 70% of the entire fluoroplastics production is PTFE. At present, polytetrafluoroethylene has been included in the list of carcinogens by the International Agency for Research on Cancer of the World Health Organization as a class 3 carcinogen.
Part 2 The water we drink
In 2016, the US Environmental Protection Agency has set the recommended limit for total PFOS and PFOA at 70 ng/L (ppt), and some states have adopted stricter standards, such as Vermont in In 2019, the standard was raised to 20 ng/L, and California proposed a standard of 5.1 ng/L. China has not yet set official standards, but the academic community has been promoting research.
1) Drinking water for Chinese residents
Tsinghua University surveyed 526 water samples from 66 Chinese cities for 18 PFASs and published its findings in Environmental Science Europe. Among them, the most seriously polluted by PFASs were Zigong, Sichuan (502.9 ng/L), Lianyungang, Jiangsu (332.6 ng/L), Changshu, Jiangsu (122.4 ng/L), Chengdu, Sichuan (119.4 ng/L), and Wuxi, Jiangsu (93.6 ng/L). /L), Hangzhou, Zhejiang (74.1 ng/L), followed by Nanning, Guangxi (64.1 ng/L), Suzhou, Jiangsu (61.3 ng/L), Kunming, Yunnan (60.4 ng/L) and Chaohu, Anhui (59.9 ng/L) .
The researchers also provided data on water samples near the plant associated with perfluorinated compounds:
The water sample of Zhonghao Chenguang Chemical Research Institute Co., Ltd. located in Zigong, Sichuan Province, which produces PTFE (Teflon), measured a PFOA value as high as 3165 ng/L. The company is a wholly-owned subsidiary of China National Chemical Corporation, and one of its main products is the Teflon mentioned in the movie. We don't know if this is the Chinese version of the DuPont incident, but what we are more worried about is that China may not have a Robert Bilot that can beat DuPont. And given China's population base and the density of the Yangtze River, the tens of thousands of people in the United States in the movie will be our tens of millions of Chinese.
Another named Jiangxi Liwen Industrial PFOA was also measured with an astonishing value of 268, and Zhejiang Juhua, a listed company with a stock code of 600160, measured 115.4ng/L in PFOA. "The DuPont factory in Guangdong was measured with a PFOA value of 53.4.
On the issue of drinking water for residents, if the 2019 standard of Vermont is used to judge, then 39 of the 66 Chinese cities have an RQ (judging the health risk of drinking water) less than 0.1, which belongs to the category of small to negligible risk, and 24 cities belong to In addition, Zigong in Sichuan, Lianyungang in Jiangsu, and Jiujiang in Jiangxi are high-risk areas. Residents' drinking water in southwest China is most seriously polluted by PFASs, with eastern China being the second most serious area, followed by cities in southern China. Except for some cities in the Bohai Rim, cities in northern China are generally less polluted.
The composition of PFASs in drinking water of Chinese residents is dominated by PFBA, PFOA and PFOS. In 2020, the TWI standard (Tolerable Weekly Intake) given in Europe for the set of FOA, PFOS, PFHxS and PFNA is 4.4ng/kg body weight. This value is from the 2008 European standard tolerable daily intake of 1500 ng /kg is reduced to the current weekly allowable intake of 4.4 ng/kg. This standard is not to say that if you take 4.4, you will be fine, but to say that you must not take it if you can.
Of the 66 cities, 20% belonged to the city limits where residents' drinking water intake of PFASs exceeded the standard. The daily intake of PFOA in all age groups in Zigong, Jiujiang, Lianyungang, Foshan, Suzhou, Wuxi, Haining, Changshu, Shijiazhuang, Zibo, and Shanghai exceeded 3 ng/kg/day (2018 US standard). In Lianyungang, Dongguan, Shenzhen, Shijiazhuang, Wuxi, Hong Kong, Taipei, Foshan, Guangzhou, Jinan, Chaohu, and Changshu, the daily intake of PFOS was between 1.27 and 61.44 ng/kg/day, but for 9 For infants aged 1 month to 1 year, the daily intake of PFOS is 3.54 to 171.28 ng/kg/day, which is far more than 2 ng/kg/day (2018 US standard). In particular, the daily intake in Zigong City is 822.9 to 2975.1ng/kg/day. It exceeds the standard of the American Agency for Toxic Drugs and Disease Registry (ATSDR) by nearly a thousand times. If this is not black water, you tell me, it is what is it?
The Tsinghua research team calculated through the city of water samples that there are 98.5 million people in China who have excessive intake of PFASs in drinking water.
However, in addition to the 66 cities involved in the research of Tsinghua University, other research teams have also conducted research on other cities. For example, the National Geological Experiment Testing Center has detected a total of 11 species in water samples from the Yangtze River Basin-Jiangxi section. PFASs, of which the detection rate of PFOA was 100%. The concentration of PFASs in surface water ranged from 7.8 to 586.2 ng/L. In general, the pollution level in the middle reaches is higher than that in the lower reaches, the main stream is higher than the tributaries, and Nanchang is higher than Poyang Lake; the main stream and tributaries of the Yangtze River are dominated by PFOA, while Nanchang and Poyang Lake are dominated by short-chain PFBS. It shows that there are differences in the main sources of pollutants in different regions. The concentration of PFASs in the surface water of Nanchang City was the highest, ranging from 146.2 to 586.2 ng/L, which was higher than other high pollution areas reported previously.
In this way, more than 100 million people in China belong to those with excessive drinking water intake of PFASs.
2) Groundwater, soil and sediment.
According to the paper by Mr. Liu Qing of Lanzhou Jiaotong University, there are still high concentrations of PFCs in the Pearl River Delta region. High concentrations of PFCs were detected in the leachate of two landfills in Guangzhou and Shenzhen. The total concentrations of leachate from the Guangshen landfill were 735.4ng/L and 338.2ng/L, respectively, with PFOA, PFOS and perfluorononanoic acid (PFNA) as the main target pollutants.
The total concentration of 13 kinds of PFCs in the sewage from 6 sewage treatment plants collected in the Pearl River Delta region ranged from 2.75 to 94.58 ng/L, and the main PFCs pollutants were perfluorooctane carboxylic acid (PFOA) and perfluorooctane sulfonate. Acid (PFOS), the total concentration of PFCs in the activated sludge was between 6.56 and 26.68 ng/g, and PFOS was the main target substance.
100% of the groundwater sampling points in Guangzhou, Zhongshan, Shenzhen, Dongguan and Qingyuan cities in the Pearl River Delta city detected PFCs pollution, and the total PFCs concentrations detected in groundwater ranged from 0.056 to 54.07ng/L. The target substances detected in groundwater are mainly perfluorocarboxylic acids and sulfonic acids with short and medium carbon chains, and the detection rate of long carbon chains is low. There was a significant correlation between the concentrations of PFCs detected in all groundwater sampling points in the Pearl River Delta region (P<0.05), indicating that these pollutants may have similar pollution sources.
Therefore, the sources of PFCs pollution in the Pearl River Delta region are typical pollution sources such as landfill leachate, sewage treatment plants and urban sewage rivers.
In November 2019, the NDRC listed perfluorooctane sulfonic acid (PFOS) and perfluorooctane sulfonyl fluoride (acceptable use as restricted) as backward products under the Stockholm Convention on Persistent Organic Pollutants.
3) What to Do If There Is a PFOA/PFOS Water Advisory
In 1944, the NSF (National Sanitation Foundation) was established at the University of Michigan School of Public Health and began to standardize public health and food safety requirements. The transparent, consensus-based standards development process that led to NSF International developing its first standards for soda coolers and light meal equipment has shaped NSF International's process for developing other public health and safety standards. To date, NSF has developed more than 80 American National Standards for public health and safety. In 1990, NSF officially changed its name to NSF International and continues to serve the food, water, environment and consumer goods sectors.
NSF International's official website specifically points out that if you find that your residential water contains excessive amounts of perfluorinated compounds, never boil the water to drink it. This is closely related to the habits of the Chinese, so special attention should be paid to it. Boiling water containing PFOS/PFOS actually concentrates contaminants. If possible, also consult your local water authority for recommendations on drinking, cooking, bathing, dishwashing, pet drinking or filtered water. The official website of NSF International provides NSFP473 certification (removal of PFOA perfluorooctane acid and PFOS perfluorooctane sulfonic acid) related enterprise certification. If you have friends who need to buy water purifiers, you can go to the official website to verify the qualifications of the other party.
Part 3 The world of beauty
With more than 4,800 known PFASs in commercial use for decades, a health crisis is brewing. Regulatory guidelines and restriction requirements vary around the world. As new PFASs are discovered in the environment and more toxicological information becomes available, stricter regulations are bound to come. The Ministry of Ecology and Environment of China Announcement No. 10 of 2019 "Announcement on Prohibiting the Production, Circulation, Use and Import and Export of Persistent Organic Pollutants such as Danlin" stipulates that PFOS and its salts shall not be used in substances and products. In the national food safety standard (GB 31604.35-2016), specific regulations are made for the determination of PFOS and PFOA in food contact materials and products, the detection limit is 1.0 ng/g, and the quantification limit is 2.0 ng/g.
Per- and polyfluoroalkyl substances (PFAS) are persistent and potentially toxic when added to cosmetics to improve durability and water resistance. However, my country's "Catalogue of Used Cosmetics Raw Materials" and "Catalogue of Cosmetics Prohibited Raw Materials" currently have no guidance on perfluorinated compounds.
The U.S. Food and Drug Administration (FDA) offers a reporting system called the Voluntary Cosmetic Registration Program (VCRP) for use by manufacturers, packers, and distributors of cosmetic products for commercial distribution in the United States. According to this VCRP system information, about 21 PFAS were repeatedly used as cosmetic ingredients during the nine-month period of 2019-2020. The labels of cosmetic products sold to consumers through the retail channel are in descending order of dominance. Some common PFAS used as cosmetic ingredients include PTFE (polytetrafluoroethylene), perfluorooctyltriethoxysilane, perfluorononyldimethyl ether, perfluorododecane, and perfluorohexane. PFAS are widely used in cosmetics, including lotions, cleansers, nail polishes, shaving creams, foundations, lipsticks, eyeliners, eye shadows, and mascaras. These PFAS are used in cosmetics to condition and smooth the skin, make it look radiant, or affect the consistency and texture of products. Also, because registration and product launch are voluntary, these data cannot be used to draw firm conclusions about the type and amount of PFAS in registered cosmetic products, nor can they be used to determine which cosmetic products may contain PFAS but are not registered in the VCRP.
However, the June 15, 2021, "Environmental Science and Technology Letters" issue of the results of a major survey by US and Canadian academics has put the eyes of the public and regulators back on PFAS. The study uses particle-induced gamma-ray emission spectroscopy. 231 cosmetic products purchased in the US and Canada were screened for perfluoro. The results show that more than half of cosmetic products sold in the United States and Canada contain fluoride. Among the eight categories tested, foundations, mascaras and lip products (lipsticks, lip balms, etc.) had the highest total fluorine content of ≥0.384 μgf/cm2. The ingredient lists of most tested products did not disclose the presence of PFAS, which exposed loopholes in US and Canadian labelling laws.
Coincidentally, in fact, as early as 2018, the EWG database has detected the problem of PFAS in 66 products of 15 cosmetic brands, including well-known big names such as Clinique.
In fact, the detection and quantification of PFAS in cosmetics is extremely challenging. Not all PFAs that may be found in cosmetic products can be easily measured because specific "fingerprints" or analytical standards for the compound may not be available. After all, concentrations of PFAS as impurities or ingredients in some cosmetic products range from 1 part per billion to 100 parts per billion. One hundred thousandth. Clearly, more research is needed for PFAS to determine:
1) Toxicological characteristics of PFOS in cosmetics;
2) The extent to which various PFAs in cosmetics can be absorbed through the skin;
3) Potential risks to human health.
In addition to cosmetics, in the jewelry and watch industry, PFAS is used in the drying process of jewelry after washing. PFPE is used as a lubricant in the watch industry, such as Rolex.
Although, on the above content, PFAS research still needs to be further clarified. But it is irrefutable that the manufacture, use and disposal of cosmetic products containing PFAS are all potential opportunities for health and ecosystem damage. Cosmetic liquids from our face washes end up in our drinking water system, and our discarded cosmetic products end up in landfills that poison the soil. PFAS is extremely difficult to degrade due to its stability. Globally, PFAS is rampant today, and in August the EU recently updated its policy on PFAS again, this time with a broader and stricter scope.
I believe that many people who read "Black Water" will re-examine whether their life and consumption are also linked to PFAS. Here are some companies that have disclosed PFAS-free policies:
Cosmetics (PFAS removal across the board): H&M (homemade product PFASfree), L'Oréal, Lumene, the Body Shop, Isadora, Kicks
Clothing (PFAS removed across the board): Valentino, Burberry, Benetton, Comptoir des Cotonniers, Esprit, H&M, Zara, Levi's, UNIQLO, Fast Retailing, Inditex, Lidl, NIKE, Li Ning, Puma, M&S, mango, Theory, G-Star, Limitedbrands, Tschibo, Tesco, Coop, C&A, Aldi, rewe, Helmut Lang, J Brand, Elvine, Kaufland, Miroglio, Primark
Fast food: Taco Bell to be completely removed by 2025. Not included in McDonald's wrapping paper, but included in bags and boxes.
Furniture (PFAS removed across the board): IKEA
Shoes: AllBirds (Mizzle products), Adidas (99% of products PFASfree), Keen (95% PFASfree; remaining 5% mostly workboots), Reebok (99% of products PFASfree)
Check out the NGO websites available for PFAS Free:
https://www.pfasfree.org.uk/current-initiatives/pfas-free-products#cosmetics
Check out the sites you must use for your cosmetic safety:
https://www.ewg.org/skindeep/
Source Retrieve from:
https://www.rsc.org/suppdata/d0/em/d0em00291g/d0em00291g1.pdf
https://pubs.acs.org/doi/pdf/10.1021/acs.estlett.1c00240
https://www.researchgate.net/publication/348417317_Per-_and_polyfluoroalkyl_substances_PFASs_in_Chinese_drinking_water_risk_assessment_and_geographical_distribution
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