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Per- and polyfluoroalkyl substances and fluorine mass balance in cosmetic products from the Swedish market: implications for environmental emissions and human exposure

Per- and polyfluoroalkyl substances (PFASs) are a diverse class of >4700 chemicals used in commercial products and industrial processes. Concerns surrounding PFASs are principally due to their widespread occurrence in humans and the environment and links to adverse health effects. One of the lesser known uses for PFASs is in cosmetic products (CPs) which come into contact with the skin (e.g. hair products, powders, sunblocks, etc.). In the present work, thirty-one CPs from five product categories (cream, foundation, pencil, powder and shaving foam) were analyzed for 39 PFASs by liquid chromatography-tandem mass spectrometry, as well as extractable organic fluorine (EOF) and total fluorine (TF) by combustion ion chromatography (CIC). This multi-platform approach enabled determination of the fraction of fluorine accounted for by known PFASs (i.e. fluorine mass balance). Foundations and powders contained 25 different PFASs with the most frequently detected being perfluorinated carboxylic acids (perfluoroheptanoic acid and perfluorohexanoic acid) and polyfluoroalkyl phosphate esters (PAPs). Σ14PAP concentrations up to 470 μg g-1 were measured in products listing mixtures of PAPs as an ingredient. For all samples, Σ39PFAS concentrations only explained a small fraction of the EOF and TF, pointing to the presence of unknown organic and/or inorganic fluorinated substances, including polymers. While creams, pencil and shaving foams did not contain measurable concentrations of any of the 39 PFASs targeted here, CIC revealed high to moderate TF content. Overall, these data highlight the need for further investigations into the occurrence of PFASs in CPs and their importance with regards to human and environmental exposure.


Introduction
Per-and polyuoroalkyl substances (PFASs) comprise a large and diverse group of synthetic chemicals which have been produced since the 1940s. Due to the strong electronegativity and small atomic size of uorine, the peruoroalkyl moiety (-C n F 2n+1 ) imparts unique properties to molecules including high surface activity, chemical and thermal stability and waterand oil-repellency. 1 These properties make PFASs useful as lowmolecular weight surfactants or polymeric materials in an array of industrial applications and consumer products. 2 However; following the detection of peruorooctane sulfonic acid (PFOS) and peruorooctanoic acid (PFOA) in human blood and wildlife samples from around the globe in 2001 there has been an increasing focus on the adverse environmental properties of PFASs. 3,4 Since the early 2000s it has been well-established that long-chain peruoroalkyl carboxylic acids (PFCAs) and peruoroalkyl sulfonic acids (PFSAs) fulll regulatory criteria for persistent, bioaccumulative and toxic substances. 5 A growing number of toxicological and epidemiological studies also suggest that elevated exposure to PFASs is related to adverse health effects in human populations. [6][7][8] Concerns regarding long-term adverse effects of PFASs have led to numerous regulatory actions and industry substitution initiatives for reducing human and wildlife exposure to PFASs. 9 A general strategy among uorochemical producers in the European Union (EU), North America and Japan has involved replacement of long-chain PFCAs, PFSAs and their precursors with shorter-chain homologues or various per-or poly-uoroether compounds 10,11 and reduction of point source emissions related to PFAS manufacture. 12,13 The industrial transition away from long-chain PFCAs and PFSAs was followed by regulatory restrictions on the quantity of these substances used in consumer products to ensure compliance by the uorochemical industry. For example, with few exceptions, it is prohibited by EU regulation to manufacture or import products containing more than 10 mg kg À1 of PFOS and its salts. 14 A similar restriction of 25 ppb of PFOA and its salts (or 1000 ppb SPFOA-related compounds) will be implemented in the EU in 2020. 15 These regulations, however, only cover a small number of the PFASs in circulation on the global market. A recent report by the Organization for Economic and Co-operation and Development (OECD) identied 4730 PFAS related CAS numbers, of which 20% are mixtures. 16 The database excludes substances with missing CAS numbers or substances under condential business information, suggesting that the actual number of PFASs might be even larger. For many of the nonregulated substances there is little information about their structure, use, exposure, toxicity, fate and associated risk(s), rendering the process of regulating these chemicals timeconsuming.
One of the lesser known uses for PFASs is in cosmetics products (CPs) which come into contact with the skin (e.g. hair products, powders, sunblocks, etc.). Examples of uorinated ingredients in CPs include: per/polyuorinated acrylate polymers, naphthalenes, alkanes/alkenes, alcohols, siloxanes, silanes, sulfonamides, ethers, esters, phosphate esters (PAPs), acrylates and acids. 17 According to the European Commission's database on cosmetic ingredients (CosIng), these substances are used in CPs as emulsiers, antistatics, stabilizers, surfactants, lm formers, viscosity regulators and solvents. 18 Regulation of PFASs included in CPs on the European market falls under the Cosmetics Regulation (Regulation (EC) no. 1223/2009) which stipulates that CP manufacturers must ensure that the contents of their products are safe for human health. 19 However, this regulation does not contain requirements on the use of substances that may impact the environment (i.e. which display persistent and bioaccumulative properties). Instead, the cosmetics regulation stipulates that environmental risks should be addressed by REACH (Registration, Evaluation, Authorization and restriction of Chemicals). REACH species that polymers and low molecular weight substances imported or manufactured in quantities of <1 tonne per year do not require hazard and risk assessments. Similarly, in the US, the Federal Food, Drug, and Cosmetic Act does not require cosmetic ingredients (with the exception of some color additives) to be approved by the Food and Drug Administration prior to entering the market. 20 While CPs are expected to be safe for consumers under their normal conditions of use, assessing the safety of their ingredients ultimately falls on the companies and individuals responsible for marketing them. Thus, PFASs used in CPs may y under the radar of both EU and North American Cosmetics regulation and REACH, either because there are no data on their risk(s) to human health or because they are used in relatively small quantities. 17 Few data are available on the occurrence of PFASs in CPs. While a recent survey of ingredients conrmed the presence of 59 different PFAS-containing CPs on the Swedish market, their concentrations remain unknown. 21 In fact, to our knowledge the only study which has quantied PFASs in CPs was that of Fujii et al. (2013) in which >87% of products sampled from Japan, Korea, France and the United States contained PFCAs. 22 However; that study only focused on a small subset of known PFASs, and not substances listed on the ingredients lists, as for example PAPs. Clearly, one of the major challenges associated with characterizing CPs (and commercial products in general) involves how to handle the large number and diversity of PFASs. While liquid chromatography coupled to tandem massspectrometry (LC-MS/MS) is the method of choice for ionic PFASs, volatile neutral PFASs and polymeric PFASs typically require analysis by gas chromatography (GC)-MS and matrixassisted laser desorption ionization time-of-ight-MS, respectively. 23,24 Despite the availability of these analytical platforms, many PFASs lack authentic standards, making them unquan-tiable using the aforementioned approaches. In order to circumvent the problems of multiple MS-based approaches and standard availability, combustion ion chromatography (CIC) 25-36 and particle induced gamma ray emission (PIGE) 28,37,38 have recently been introduced for indirect quan-tication of total and extractable organic uorine (TF and EOF, respectively) in samples. As these approaches are uorine-specic, a standard of any uorinated substance may be used for quantication. When paired with targeted PFAS analysis using e.g. LC-MS/MS, uorine mass balance calculations can be used to assess the fraction of TF and EOF explained by known PFASs, but also the fraction of as-of-yet unidentied PFASs. Early applications of CIC and PIGE in reghting foams, biota and textiles have revealed that only a small fraction of the organic uorine content can be accounted for by known PFASs. 31,33,37 The overall aim of this study was to quantify a diverse range of PFASs in CPs on the Swedish market and assess the fraction of TF and EOF accounted for by these substances. To achieve this goal we used a combination of targeted LC-MS/MS analysis and uorine-specic CIC measurements, combined with uorine mass balance calculations. To our knowledge this is the rst uorine mass balance study on CPs. The results are discussed with respect to their implications for environmental emissions and human exposure.

Sample selection
Thirty-one CPs from ve product categories were analyzed in the present work. Representative samples of PFAS-containing CPs were selected from a database of ingredient lists, compiled by the Swedish Society for Nature Conservation (SSNC). Based on the survey by KEMI in 2015, the most frequently reported PFASs reported in CPs were used to identify specic products containing these substances on their ingredient list. 17 During 2016 and 2017, 24 CPs listing 9 different PFASs as active ingredients were purchased from the Swedish market. In addition, 7 products which did not list PFASs among their ingredients were purchased from the same stores as control samples. The products included moisturizing creams (abbreviated CRE), foundations (FOUN), powders and eye shadows (POW), eye pencil (PEN) and shaving foams (SHAV). A tabular overview of the samples, brand names and uorinated ingredients (according to international nomenclature of cosmetic ingredients (INCI)) as listed on the packaging is given in Table 1.

Targeted PFAS analysis
Sample extraction and targeted analysis was carried out at Stockholm University (SU). Samples were extracted using a method adapted from Powley et al. (2005). 39 Briey, 0.5 ml of 0.2 M NaOH, 5 ml methanol and 50 ml of internal standard mixture (50 ng ml À1 ) were added to 0.1 g of sample material. Thereaer, samples were vortexed and extracted in an ultrasonic bath at room temperature for 30 minutes. Aer centrifuging at 2000 rpm for 5 minutes, the supernatant was transferred to a new test tube. The extraction was repeated with 5 ml methanol and the extract centrifuged for 20 min at 3000 rpm, aer which it was neutralized with 50 ml of 2 M HCl. The combined supernatants from both extractions were concentrated under a gentle stream of nitrogen to about 1 ml. 500 ml of the concentrated extract was transferred to a 1.5 ml Eppendorf tube containing 25 mg graphitized carbon (Supelclean ENVI-carb) and 50 ml glacial acetic acid, vortexed and centrifuged at 10 000 rpm for 10 minutes before transferring the supernatant to a new Eppendorf tube to which 50 ml of recovery internal standards (20 ng ml À1 ) and 500 ml of 4 mM aqueous NH 4 OAc solution was added. The samples were stored in the freezer until the day of analysis. Before injection, the samples were vortexed, centrifuged and transferred to a micro vial. Extracts were injected (5 ml) onto an Acquity UPLC (Waters Corp., Milford, MA) equipped with BEH C18 guard (5 Â 2.1 mm, 1.7 mm particle size) and analytical (50 Â 2.1 mm, 1.7 mm) column operated at 40 C. Mobile phase composition and details about gradient and ow rate can be found in Tables S2 and S3. † Detection of PFASs was carried out using a triple quadrupole mass spectrometer (Xevo TQ-S, Waters Corp, Milford, MA) operated in negative electrospray ionization mode according to a method reported by Gebbink et al. 40 Further information on MS parameters and MS transitions can be found in Table S1. † Quantication of individual PFASs (39 targets) was carried out using linear calibration curves (1/x weighting) ranging from 0.008 to 150 ng ml À1 .
In cases where a target exceeded the concentration of the highest point in the calibration curve (some mono-and diPAPs in samples FOUN01, FOUN02 and FOUN03), the respective extracts and blanks were subjected to three levels of dilution (1 : 5 to 1 : 500) depending on the analyte concentration followed by fortication of internal standard (10 ng) and re-analysis on LC-MS/MS. The addition of internal standards to the extracts (versus to the sample) accounts for matrix effects in the quantication; however, losses during the extraction procedure are not tracked by this approach. Generally, the concentration of an analyte in the nal extract can be adjusted either by reducing the amount of material subjected to extraction or by diluting the extract. However, in the case of samples FOUN01, FOUN02 and FOUN03, the concentrations were too high to nd a balance of sample amount and nal volume at which a reasonable amount of internal standard added to the sample would still be detectable in the diluted extract. Therefore, the concentrations reported for PAPs in those three samples are not corrected for procedural losses. Thus, these not-corrected concentrations are directly comparable to EOF concentrations, which also return concentrations in the sample extract rather than in the neat sample, and can be used directly for mass balance calculations.
The procedural blanks that were prepared and processed independently along with all samples did not show detectable contamination for any target PFAS. Therefore, the LODs were determined using the concentration obtained from the lowest calibration point with a signal to noise ratio of at least 3 and converted to w/w units using an average sample weight. LODs are summarized in Tables S8 and S9. † In case of extract dilution, the dilution factor has to be taken into account for the calculation of the LOD for the respective sample.
Analysis of total uorine and extractable organic uorine TF and EOF measurements were carried out at SU using a Thermo-Mitsubishi combustion ion chromatograph (CIC). Sample extracts (100 ml) were placed in a ceramic sample boat containing glass wool for better dispersion of the uids while neat CP material was weighed directly into the sample boat. All boats were baked prior to sample combustion to minimize background contamination. The samples were combusted slowly in a combustion furnace (HF-210, Mitsubishi) at 1100 C under a ow of oxygen (400 l min À1 ) and argon mixed with water vapor (200 l min À1 ) for approximately 5 minutes. Combustion gases were absorbed in MilliQ water during the entire length of the combustion process using a gas absorber unit (GA-210, Mitsubishi). An aliquot of the absorption solution (18 or 200 ml, depending on sample concentration) was injected onto an ion chromatograph (Dionex Integrion HPIC, Thermo Fisher Scientic) equipped with an anion exchange column (Dionex IonPac AS19 2 Â 50 mm guard column and 2 Â 250 mm analytical column, 7.5 mm particle size) operated at 30 C. Chromatographic separation was achieved by running a gradient of aqueous hydroxide mobile phase ramping from 8 mM to 60 mM at a ow rate of 0.25 ml min À1 . Fluoride was detected using a conductivity detector.
Sample sizes were approximately 5 mg of neat CP material for TF analysis (i.e. direct combustion; Fig. 1) and 0.05-0.8 g of CP material for EOF (i.e. combustion of extract; Fig. 1) depending on the expected uorine concentration. Samples intended for EOF analysis were extracted using a similar procedure as for targeted analysis described above but without addition of internal standards. The nal volume of the extract was adjusted by evaporation of the solvent to about 2 ml, with the exception of high concentration samples which were kept at a nal volume of 10 ml. In both cases, extraction blanks of the same nal solvent volume were analyzed together with the sample extracts. More information about blank monitoring and quality control procedures can be found in the QA/QC section.
Quantication of TF and EOF was carried out using a linear sixpoint calibration curve of PFOS ranging from 0.5 to 100 mg ml À1 (r 2 > 0.999). EOF extract concentrations were adjusted by dilution with methanol or solvent evaporation under nitrogen to t within the concentration range of the calibration curve. The LOD for TF measurements was calculated from three times the average area obtained from instrumental blanks (n ¼ 3) and converted using an average sample amount (3 mg) which resulted in 91.1 mg g À1 . TF method blanks were below 1% of sample concentrations, and therefore TF measurements were not blank-corrected. For EOF measurements, LODs were calculated using three times the average signal of the procedural blank (n ¼ 3) converted with the corresponding calibration curve and an average nal extract volume (2 ml) and sample amount (0.5 g). LODs for EOF measurements were determined for every batch of measurements and varied depending on the inter-day variability of the instrumental response and blank level and ranged from 1.02 to 6.65 mg g À1 . All EOF concentrations were blank corrected.

Fluorine mass balance calculations
Fluorine mass balance calculations were carried out by converting the concentration for a given PFAS measured by LC-MS/ MS (C PFAS ; ng PFAS per g) to its corresponding uoride concentration (C F_PFAS ; ng F per g) using the following equation: where n F is the number of uorine atoms on the molecule, A F is the atomic weight of uorine and MW PFAS is the molecular weight of the PFAS. The total known extractable uorine concentration (SC F_PFAS ; ng F per g) is obtained by summing the uorine concentrations from all individual PFASs. The total concentration of unidentied, extractable organic uorine (C F_extr.unknown ; ng F per g) can then be determined by subtracting SC F_PFAS from the total extractable organic uorine concentration (C F_EOF ; ng F per g) as measured directly by CIC, according to eqn (2).
The total uorine concentration (C F_TF ; ng F per g) as measured directly by CIC equals the sum of C F_EOF and the total non-extractable uorine concentration (C F_non extr. ; ng F per g), as shown in eqn (3).
(3) In addition to assessing accuracy and precision of the method for EOF, these experiments served to evaluate whether inorganic uorine (NaF) was removed during the extraction procedure. The accuracy and precision of TF measurements were assessed through triplicate combustions of a certied reference material (CRM) (BCR®-461, uorine in clay). In addition to the aforementioned method validation, three extraction blanks were processed along with every batch, and QC standard and blank injections were performed intermittently to assess instrument dri and carryover, respectively (both LC-MS/MS and CIC). Intra-sample variability of TF and EOF was assessed by analyzing 20% of samples in triplicate (CIC). As a nal validation of the method, 18 unfortied samples were re-analyzed for 11 PFASs by IVL Swedish Environmental Institute (IVL) and compared to results generated by SU.

Results and discussion
Targeted PFAS analysis Method accuracy, as assessed through spike/recovery experiments, ranged from 71 to 126% for most PFASs (Table S4 †  recoveries (up to 280%) and PFTrDA, FOSAA and 6:2/8:2 diPAP which displayed lower recoveries (as low as 29%), likely due to matrix-induced ionization effects (since qualier ions displayed similar recoveries) which were not accounted for due to the absence of exactly-matched isotopically labelled standards. Nevertheless, most substances displayed good precision (average RSD of 24%) at both fortication levels (Table S4 †).
Results of the inter-laboratory comparison on a subset of 18 samples (unfortied) revealed good agreement between labs, with a coefficient of determination of 0.9605 for 11 targeted PFAS measurements (Fig. S1 †).
In total, 16 out of 31 samples contained measurable concentrations of at least one PFAS (see Fig. 2, Tables S7 and S8 † for a full list of concentrations). Foundation and powder products contained up to 25 out of 39 monitored PFASs above detection limits, whereas samples of cream, pencil and shaving foam did not contain detectable concentrations of targeted PFASs. Samples not listing uorinated ingredients were below LOD for all PFASs. The highest detection frequency was observed for short-chain PFCAs (PFHpA 39%, PFBA 35%, PFHxA 32%, PFPeA 29%). Six long-chain PFCA homologues were detected above the LOD (in order of decreasing detection frequency: PFUnDA > PFOA ¼ PFDA ¼ PFDoDA > PFNA > PFTrDA). S 10 PFCA concentrations ranged from <LOD to 9220 ng g À1 for foundations and from <LOD to 679 ng g À1 for powders and eye shadows. Although PFCAs were the most frequently detected compounds, some mono-and diPAPs were detected in far higher concentrations (up to 405 mg g À1 ). The dominant chain lengths for PAPs were 6:2 and 8:2, albeit homologues from 4:2 up to 12:2 were also detected. S 14 PAP concentrations ranged from <LOD to 471 mg g À1 for foundations and from <LOD to 282 ng g À1 for powders and eye shadows. Additionally, 6:2 and 8:2 FTSA were detected in three (FOUN01, FOUN02 and FOUN03; 21.9 to 132 ng g À1 ) and one (FOUN03, 156 ng g À1 ) foundation products, respectively. No peruoroether carboxylic acids, PFSAs or related precursors were detected above LODs in any sample.
Three samples (FOUN01, FOUN02 and FOUN03) contained particularly high concentrations of PAPs and PFCAs (see Fig. 2), with S 39 PFAS concentrations of 319, 229 and 479 mg g À1 , respectively. The major PFASs in these samples were 6:2/6:2 diPAP (256, 63.7 and 405 mg g À1 , respectively) and 6:2 monoPAP (55.5, 50.4 and 62.0 mg g À1 , respectively), accounting for 98% (FOUN01 and FOUN03) and 50% (FOUN02) of S 39 PFAS. The nding of PAPs in these samples is in agreement with the ingredients lists, which specify ammonium C6-16 per-uoroalkylethyl phosphate (FOUN01 and FOUN03) and C9-15 uoroalcohol phosphate (FOUN02) as intentionally added components (INCI nomenclature). The co-occurrence of PFCAs (S 10 PFCA concentrations 4890, 9220 and 8480 ng g À1 respectively) and FTSAs (S 3 FTSA concentrations of 21.9, 288 and 60.6 ng g À1 , respectively) in these samples is, however, more likely due to impurities in the technical mixture of PAPs or degradation of the active ingredients, since they are found in relatively low concentrations. Several other studies have demonstrated the presence of PFCAs as impurities in products treated with uorotelomer-based substances. [41][42][43][44][45] Our ndings of PFCAs in cosmetics were in good agreement with a previous study by Fujii et al. (2013) who reported S 9 PFCA concentrations of up to 5900 ng g À1 in foundations collected from the Japanese market in 2009 and 2011. 22 However, the Japanese products displayed a slightly different homologue pattern with consistently higher concentrations of PFOA compared to PFHxA. The overall higher concentrations and detection frequency of PFHxA in this study probably reect the industrial transition from C8 to C6 uorotelomer-based PFASs occurring in the period between when the two studies were conducted. Thus, the homologue pattern of PFASs in cosmetics appear to follow the same trend as treated textiles and papers where recent studies typically report the highest concentrations and detection frequency for C6 compounds. 37,38,46 Fluorine mass balance and unidentied PFASs CIC spike/recovery experiments involving samples fortied with different combinations of PFOS and NaF (see method section for details) revealed that inorganic uorine was effectively removed during the extraction procedure (i.e. uorine was not detected in samples fortied only with NaF). This was remarkable as previous studies had found it necessary to use a solid phase extraction step for efficient removal of inorganic uorine. 25,31 Furthermore, PFOS fortied into foundation or blanks revealed reasonable accuracy and precision, given that no internal standard was used to account for losses during the extraction procedure (recovery of 69 AE 14% RSD, n ¼ 3 replicates for spiked foundation and blanks, see Table S6 †). Validation of TF measurements via direct combustion of the CRM (BCR®-461, uorine in clay) revealed excellent agreement between measured (565 AE 15 mg kg À1 , n ¼ 3) and certied concentrations (568 AE 60 mg kg À1 ). Finally, intra-sample variability (assessed via triplicate measurements of 20% of samples) averaged 10% for TF and 3% for EOF measurements. The larger intra-sample variability for TF compared to EOF measurements may be attributed in part to the uncertainty of weighing small amounts of neat product material and potential heterogeneity of the small aliquots.
Twenty-three out of the 24 samples listing uorinated ingredients produced TF measurements >LOD, while EOF concentrations were above LOD for 17 samples (Fig. 3 and Table  S9 †). Overall, TF and EOF content showed high variability within each product category. The highest TF concentrations were found in powders (547-19 200 mg g À1 ), closely followed by creams (<LOD -11 100 mg g À1 ) and foundations (326-3120 mg g À1 ). Pencil and shaving foams displayed lower TF concentrations (438 and <LOD -837 mg g À1 , respectively). As expected, EOF concentrations were consistently lower than TF, accounting for 0-55% of the total uorine (averaging 9%). In contrast to TF concentrations, the highest EOF concentrations were measured in foundation samples (1.29-1720 mg g À1 ).
FOUN01, FOUN02 and FOUN03, which displayed the highest S 39 PFAS concentrations, also showed high TF (3120, 2900 and 2570 mg g À1 respectively) and EOF concentrations (1720, 1380 and 1050 mg g À1 respectively). In these samples, SC F_PFAS accounted for 11, 10 and 28% of C F_EOF respectively, which in turn accounted for 55, 48 and 41% of C F_TF (Fig. 3). According to eqn (2), the total concentration of unidentied, extractable organic uorine C F_extr.unknown amounts to 1520, 1240 and 754 mg g À1 respectively. Here it is germane to note that for these three samples, concentrations of PAPs (which represented the major fraction of characterized EOF) were not corrected for procedural losses (see explanation in Methods section). Consequently, SC F_PAP (accouting for 98% of SC F_PFAS ) and C F_EOF (which also is not corrected for procedural loss) are For the remaining samples, the fraction of C F_EOF accounted for by SC F_PFAS was negligible (#1.3%), with remaining C F_extr.unknown of up to 552 mg g À1 . As in these cases all PFAS concentrations were adjusted for extraction losses while EOF concentrations are not, the gap between C F_EOF and SC F_PFAS (C F_extr.unknown ) should be considered conservative (i.e. underestimated). However, as the listed uorinated ingredients in these samples (peruorooctyl triethoxysilane, triuoropropyl dimethiconol, peruoropropyl dimethicone, and polymers polytetrauoroethylene (PTFE, also known as Teon, polytefum or polytef), polyperuoromethylisopropyl ether, triuoroacetyl tripeptide-2 and polyperuoroethoxymethoxy diuoroethyl PEG phosphate) were not quantied due to lack of analytical methods and standards, the signicance of C F_extr.unknown in these samples remains unclear. Notably, the four samples listing peruorooctyl triethoxysilane (FOUN05, POW06, POW09 and POW12) all contained C4-C7 PFCAs, dominated by the C6 homologue. These PFCAs are presumably impurities or degradation products of the 6:2 uorotelomer moiety of the per-uorooctyl triethoxysilane, given that they did not appear on ingredients lists. Overall these data indicate that uorinecontaining ingredients do not necessarily account for all of the measured EOF, and that other PFASs not included in ingredient lists may be important.
One of the study limitations was that some of the listed uorinated ingredients (e.g. uorinated silanes, polymeric substances) were not quantied due to the lack of MS-based methods and/or authentic standards. In those cases, the mass balance gap between S 39 PFASs and EOF may be explained by the active ingredient. However, some of these CPs contained PFASs impurities which are not likely to originate from the listed uorinated ingredient and might therefore indicate the presence of other PFAS or PFAS precursors in these products. Samples in which the active ingredient was quantied (i.e. PAPs) still showed a large gap between S 39 PFASs and EOF, hinting at the presence of other uorinated substances that were not included in the targeted analysis. Similarly, TF and EOF concentrations were signicantly different in all samples with the EOF content only accounting 9% of TF on average. This difference reects on one hand the extraction efficiency of low molecular substances (e.g. PAPs) and on the other hand the presence of non-extractable substances such as polymers or inorganic uorine (e.g. uoride or uorphlogopite).

Implications for human exposure and environmental emissions
This study demonstrates that PFCAs of various chain-lengths are present in CPs as impurities or degradation products of other PFASs which are added as active ingredients. Dermal exposure to PFCAs has, thus far, been considered negligible relative to contributions from dietary intake, drinking water and ingestion of house dust according to current human exposure assessments. 47,48 However, these exposure assessments have not considered the potential contribution of CPs towards dermal uptake due to the lack of measurement data. Furthermore, the assessments for other types of consumer products (e.g. PFAStreated textiles and impregnation sprays) may have underestimated the exposure by using the dermal absorption coefficients for the ammonium salt of PFOA 49 without consideration of how ionization status, co-solvents etc. may affect dermal penetration. Thus, the results from this study on PFASs in CPs in combination with more recent dermal permeability studies of PFOA underscore the need to revisit the potential contribution of dermal exposure. 50 Considering that foundations displayed the highest detection frequency and absolute concentrations of PFASs the following calculation illustrates the potential importance of dermal exposure to PFASs. According to the US EPA exposure factors handbook the amount of foundation per application is 0.265 gram. Assuming a daily application of foundation, a body weight of 60 kg and that 30% of the applied PFOA has penetrated the skin aer 10 hours (ref. 50) the estimated daily exposure to PFOA from CPs analyzed in this study would be in the range <0.006-3.1 ng per kg per day. The higher-end values indicate that frequent application of specic CPs can lead to a dermal exposure to PFOA which exceeds daily intakes of PFOA via diet (0.04-0.7 ng per kg per day) for the Swedish population. 51,52 It should also be noted that these calculations do not consider indirect exposure to PFOA via metabolism of PAPs, which were present in 100-fold higher concentrations compared to PFCAs, or other potential precursors that contributed to the EOF fraction. Clearly, more research is needed to establish dermal absorption coefficients for a wider range of PFASs and application conditions and the potential transformation of PFASs by phase 1 and phase 2 enzymes and photolytic processes in or on the skin. [53][54][55] In addition to the potential for human exposure, there may be environmental risks associated with PFASs in CPs which enter waste streams following use. It is unclear how these substances will behave during wastewater treatment. However, waste water treatment plants (WWTPs) have been identied as a signicant source of PFASs, either to air, receiving water, and elds where sludge is applied as fertilizer. 56,57 A recent uorine mass balance study of Swedish WWTPs reported that 42-82% of extractable organic uorine in sludge and 5-21% in effluent were unaccounted for. Notably, diPAPs, which are among the known ingredients in some CPs, contributed a major proportion (63%) to the SPFAS concentrations in sludge samples. 57

Conflicts of interest
The authors have no conicts of interest to declare.