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Environmental Research 111 (2011) 329–336

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Environmental Research
journal homepage: www.elsevier.com/locate/envres

Phthalates in cosmetic and personal care products: Concentrations and


possible dermal exposure
Diane Koniecki a, Rong Wang b, Richard P. Moody b, Jiping Zhu b,n
a
Cosmetics Division, Health Canada, Ottawa, Canada
b
Exposure and Biomonitoring Division, Health Canada, Ottawa, Canada

a r t i c l e i n f o abstract

Article history: Phthalates are multifunctional chemicals that are used in a variety of consumer products including
Received 12 June 2010 cosmetic and personal care products. This study aims at determining phthalate levels in cosmetic and
Received in revised form personal care products obtained from the Canadian market. Overall 252 products including 98 baby
14 January 2011
care products were collected at retail stores in several provinces across Canada in year 2007. These
Accepted 18 January 2011
products included fragrances, hair care products (hair sprays, mousses, and gels), deodorants (including
Available online 18 February 2011
antiperspirants), nail polishes, lotions (body lotions and body creams), skin cleansers, and baby
Keywords: products (oils, lotions, shampoos and diaper creams). Samples were extracted with different organic
Phthalates solvents, depending on the types of the products, followed by gas chromatography-mass spectrometry
Cosmetic
(GC–MS) analysis. Of the 18 investigated phthalates, diethyl phthalate (DEP), dimethyl phthalate
Dermal exposure
(DMP), diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP) and di(2-ethylhexyl) phthalate (DEHP)
GC/MS analysis
were detected. The detection frequencies were in the following order: DEP (103 out of 252
products) 4DnBP (15/252)4 DiBP (9/252) 4 DEHP (8/252)4 DMP (1/252). DEP was detected in almost
all types of surveyed products with the highest levels (25,542 mg/g, equal to 2.6%) found in fragrances.
DnBP was largely present in nail polish products with the highest concentration of 24,304 mg/g (2.4%).
DnBP was also found in other products such as hair sprays, hair mousses, skin cleansers and baby
shampoos at much lower concentrations (36 mg/g and less). Levels of other detected phthalates were
generally low in the products. Based on these values, daily dermal exposure dosage to five phthalates
was estimated for three age groups, female adults (60 kg); toddlers (0.5–4 years) and infants (0–6
months), through the use of cosmetic and personal care products. The exposure estimation, however,
was based on existing products use pattern data, instead of probabilistic model based population use
distribution. For female adults, the maximal daily exposure of 78 mg/kg bw/d was determined for DEP.
The maximal daily exposure was much lower for the other four phthalates (DEHP, 0.82 mg/kg bw/d;
DnBP, 0.36 mg/kg bw/d; and DMP, 0.03 mg/kg bw/d). The exposure for DiBP was not calculated due to its
very low levels (o 10 mg/g) in products. Toddlers and infants in this case had a maximal daily exposure
to DEP of 20 and 42 mg/kg bw/d, respectively.
Crown Copyright & 2011 Published by Elsevier Inc. All rights reserved.

1. Introduction lacquers, latex and paste paints (B+ S Chemie, 2000), and in nail
polish.
Phthalates (also called phthalic acid esters) have been widely Due to their widespread use, phthalates have been detected in
used in modern society. Phthalates with higher molecular the environment (Wormuth et al., 2006), foodstuff (Benson,
weights, such as di(2-ethylhexyl) phthalate (DEHP) (Table 1) are 2009), consumer products (Heudorf et al., 2007; Schettler,
principally used as additives and plasticizers in polyvinyl chloride 2006), indoor and personal air (Adibi et al., 2008; Xu et al.,
plastics (PVC), while those with lower molecular weights, such 2010; Destaillats et al., 2008), indoor dust (Bornehag et al.,
as diethyl phthalate (DEP), di-n-butyl phthalate (DnBP), and 2005; Deutschle et al., 2008; Koralik et al., 2008; Schripp et al.,
dimethyl phthalate (DMP), are employed in solvent, adhesive, 2010), and air inside vehicles (Geiss et al., 2009). The general
wax, ink, pharmaceutical, cosmetic and insecticide production population may be exposed since phthalates are ubiquitous
(Schettler, 2006). An additional plasticizer for PVC, diisobutyl environmental contaminants (Wittassek and Angerer, 2008;
phthalate (DiBP) is used as a light-resistant plasticizer for Hauser and Calafat, 2005). Presence of phthalates in human breast
milk was reported in Canada (Zhu et al., 2006), the United Sates
(Hines et al., 2009), Japan (Takatori et al., 2007), Denmark/Finland
n
Corresponding author. (Main et al., 2006)), and Italy (Latini et al., 2009). A number of
E-mail address: jiping.zhu@hc-sc.gc.ca (J. Zhu). human biomonitoring studies on the monoesters of phthalates has

0013-9351/$ - see front matter Crown Copyright & 2011 Published by Elsevier Inc. All rights reserved.
doi:10.1016/j.envres.2011.01.013
330 D. Koniecki et al. / Environmental Research 111 (2011) 329–336

Table 1
Physical properties of phthalates that were detected in the tested products.

Chemical (CAS no.) Formula Molecular Boiling Vapor pressure Water solubility Log Henry’s Law Constant
weight point (1C) (mmHg at 25 1C) (mg/L at 25 1C) Kow (atm m3 /mole at 25
1C)

DMP (131-11-3) C10H10O4 194.2 283.7 3.08  10  3 4000 1.6 1.07  10  7


DEP (84-66-2) C12H14O4 222.2 295 2.1  10  3 1080 2.42 6.10  10  7
DiBP (84-69-5) C16H22O4 278.4 296.5 6.65  10  3 6.2 4.11 1.22  10  6
DnBP (84-74-2) C16H22O4 278.4 340 2.01  10  5 13 4.5 1.81  10  6
DEHP (117-81-7) C24H38O4 390.6 385 7.23  10  8 0.285 7.6 4.37  10  5

Log Kow¼ logarithm of octanol–water partition coefficient. Values are from the NIOSH (2009).

highlighted the large extent of humans exposure to various phtha- to reproduction (category 2 substances should be regarded as if
lates (Blount et al., 2000; CDC, 2005; Calafat and McKee, 2006; Koch they impair fertility, or if they cause developmental toxicity in
et al., 2005; Wittassek and Angerer, 2008). In parallel to the humans (Rank, 2005). DEHP is currently listed on Health Canada’s
measurements in urine, phthalates and their metabolites were also Cosmetic Ingredient Hotlist as a prohibited ingredient and should
detected in blood serum, saliva (Hines et al., 2009; Koch et al., 2005; not be used in cosmetic products (EC, 2009a). DEP is not regulated
Högberg et al., 2008) and amniotic fluid (Wittassek et al., 2009). in Canada or in any other countries.
Evidence has accumulated for the association of harmful health Exposure guidance values, which are estimates of daily exposure
effects with exposure to phthalates and their monoester metabolites that are likely to be without an appreciable risk of deleterious effects,
(Latini et al., 2004; Hauser and Calafat, 2005; Foster, 2006; Lyche are also being developed for certain phthalates. The available gui-
et al., 2009). Main health concerns relating to phthalates are based on dance values for DEP, DiBP, DnBP, and DEHP derived from toxicolo-
animal studies which showed that exposure to certain phthalates can gical studies conducted in animals administered through the oral
cause adverse health effects including effects on development of the route are presented in Table 2, since dermal data were lacking.
male reproductive system (Foster, 2006; Benson, 2009). DnBP and Tolerable daily intake (TDI) values of 0.044 mg/kg bw/d and
DEHP have effects on germ cell development, and butylbenzyl 0.063 mg/kg bw/d were established for DEHP and DnBP by Health
phthalate affects epididymal spermatozoa concentration (Foster Canada, respectively (EC/EC, 1994a, 1994b). More recently, the
et al., 2000; Christiansen et al., 2008). Anti-androgenic effects of European Food Safety Authority (EFSA, 2005a) allocated a TDI of
DnBP, DEHP, DiBP, butylbenzyl phthalate and diisonyl phthalate have 0.048 mg/kg bw/d for DEHP based on reproductive effects and a TDI
been observed in fetal rats (Mylchreest et al., 1998; Grandjean and of 0.01 mg/kg bw/d for DnBP for developmental toxicity in male
Toppari, 2006; Borch et al., 2006; NRC, 2008). A more recent study rodents. For DiBP, the oral reference dose (RfD) of 0.8 mg/kg bw/d
demonstrated dose-additive effects on testosterone reduction in the (Benson, 2009) is based on a benchmark dose level (BMDL) for
fetal testes (Howdeshell et al., 2008). DEP and DMP, however, have toxicity to the developing male rat reproductive system (Howdeshell
not been shown to be reproductive or developmental toxicants (Gray et al., 2008). The RfD of 0.8 mg/kg bw/d for DEP is deduced on a no-
et al., 2000; Benson, 2009). Human data on health effects of observed adverse effect level (NOAEL) of 750 mg/kg bw/d for changes
phthalates are limited and often inconclusive (Hauser and Calafat, in growth rate and organ weights in rats (U.S. EPA, 1993).
2005; Gwinn et al., 2007; Janjua et al., 2007; Jakkola and Knight, Only limited information on the levels of phthalates in cosmetic
2008; Swan et al., 2005; Kamrin, 2009). Some evidence supports the and personal care products and potential human exposure through
hypothesis that exposure to phthalates in the home environment use of these products is currently available (NRC, 2008). Koo and Lee
increases the risk of adverse effects on airways and immunologic (2004) monitored several phthalates including DEHP, DEP and DnBP
system (Koralik et al., 2008; Deutschle et al., 2008; Bornehag et al., in cosmetics purchased at retail in Korea. The sample consisted of 102
2004, 2005). A British epidemiologic study found a link between products of four categories (perfumes, deodorants, nail polishes and
phthalates in the home and the development of allergy and asthma in hair care). A non-profit organization Environmental Working Group
children, but the evidence was limited by imprecise data on levels of found phthalates in 52 of the 72 tested off-the-shelf cosmetic and
exposure (Jakkola and Knight, 2008). Large amounts of specific personal care products including deodorants, fragrances, hair gels,
phthalates fed to rodents have been shown to damage their liver, mousses, hair sprays, and hand and body lotions (Houlihan et al.,
kidneys, thyroid gland tissue, and initial rodent studies indicated 2002). A study commissioned by Greenpeace (2005) reported phtha-
hepato-carcinogenicity. However, further research indicated that the lates in perfumes sold on the European market. DEP was found in 35
mechanism of liver tumors is specific to rodents and led to the of the 36 tested perfume products with the highest concentration of
conclusion that DEHP is not likely to be carcinogenic in humans. 2.23%. DMP levels were reaching 0.3%. Other phthalates were
(IARC, 2000). detected, in very small quantities which led the European Commis-
Concerns over health effects of phthalates as a group, particu- sion’s Scientific Committee on Consumer Products (SCCP) to the
larly on reproduction, have drawn attention from both the conclusion that they were likely present as traces or impurities
advocacy groups and lawmakers, especially given the fact that (SCCP, 2007). Whether DMP was intentionally used as an ingredient,
phthalate exposure is ubiquitous in the general population however, could not be concluded. Hubinger and Harvey (2006) also
(Heudorf et al., 2007; Duty et al., 2005; Wormuth et al., 2006). reported phthalates in 48 cosmetic and personal care products for the
Policies and regulations restricting the use of phthalates have general population in the US market. The objective of the present
been developed in various jurisdictions. For example, the United study was to conduct a national survey on the level of phthalates in
States and the European Union are currently regulating several cosmetic and personal care products on the Canadian market to
phthalates including DEHP and DnBP in children’s products, and document the potential levels of exposure to phthalates related to the
similar action is underway in Canada (EC, 2009b). The European use of cosmetic and personal care products in Canada. A total of 18
Union has banned DnBP and DEHP for use in cosmetic and phthalates (for target list, see Technical Appendix) were monitored in
personal care products in the European market (SCCP, 2007), 252 cosmetic and personal care products including 98 baby care
both are classified in the European Union as category 2 substances products collected in several Canadian provinces.
D. Koniecki et al. / Environmental Research 111 (2011) 329–336 331

Table 2
Health-based exposure guidance values for phthalates from various committees.

Chemical Critical endpoint and (reference) study Committee and POD/UFa Guidance value
year of evaluation (mg/kg bw/day)

DMP Not available


DEP NOAEL¼ 750 mg/kg bw/d for decreased growth rate, food U.S. EPA (1993) NOAEL/1000 RfD 0.8
consumption and altered organ weights in a rat subchronic
oral feeding study (U.S. EPA, 1993)
DiBP NOAEL¼ 100 mg/kg bw/d for decreased fetal testosterone BMDL/100 RfD 0.8
production in male rats (Howdeshell et al., 2008) and derived
a BMDL 1 SD of 80 mg/kg bw/d (Benson, 2009)
DnBP NOAEL¼ 30 mg/kg bw/d based on decreased fetal testosterone US EPA (2006) NOAEL/100 RfD 0.3
production (Lehmann et al., 2004)
NOAEL¼ 62.5 mg/kg bw/d based decreases in live offspring and Health Canada NOAEL/1000 TDI 0.063
increases in external defects and skeletal anomalies in mice (1994a)
(Chan and Meek, 1994)
LOAEL¼ 2 mg/kg bw/d for loss of germ cell development and EFSA (2005b) LOAEL/200 TDI 0.01
mammary gland changes in rats exposed during gestation and
lactation (Lee et al., 2004)
DEHP LOAEL¼ 19 mg/kg bw/d for increased relative liver weights in U.S. EPA (1991) LOAEL/1000 RfD 0.02
suchronic to chronic oral exposure of guinea pigs (U.S. EPA, 1991)
NOAEL¼ 44 mg/kg bw/d for increased numbers of malformed Health Canada NOAEL/1000 TDI 0.044
fetuses (Meek and Chan, 1994) (1994b)
NOAEL¼ 4.8 mg/kg bw/d for testicular and developmental EFSA (2005a) NOAEL/100 TDI 0.048
toxicity (Wolfe and Layton, 2003)
ECB (2008) NOAEL/250 TDI 0.020 for newborn 0–3
months old, women in
childbearing age
NOAEL/200 TDI 0.025 for infants 3–12
months old

TDI, tolerable daily intake; RfD, reference dose; BMDL, benchmark dose level; bw, body weight; NOAEL, no-observed-adverse-effect-level; LOAEL, lowest-observed-
adverse-effect-level.
a
POD/UF, point of departure/uncertainty factor.

Table 3
Mean recoveries (with relative standard deviation in bracket) of spiked internal standards from different types of products with their respective extraction method.

Product type Spiking DMP-d4 DnBP-d4 DEHP-d4 Extraction


level (mg/g) method

Fragrance, hair care (except hair gel), deodorant, 100 88% (20%) 99% (21%) 87% (23%) Extraction with hexane only
baby products (except shampoo and lotion)
Lotion, skin cleanser, shampoo, and hair gel 100 93% (16%) 100% (19%) Extraction with water first, then hexane
Lotion, skin cleanser, shampoo, and hair gel 100 94% (23%) Extraction with methanol first, then hexane
Nail polish 100 79% (21%) 99% (23%) 99% (10%) Extraction with acetone first, then hexane

DMP ¼dimethyl phthalate; DnBP¼ di-n-butyl phthalate; DEHP¼ di(2-ethylhexyl) phthalate.

2. Experimental recoveries for phthalates (Table 3). For lotions, skin cleansers,
shampoos, and hair gels, two different solvent systems were used
2.1. Samples and chemicals in order to obtain high recoveries for both short chain (DMP and
DnBP) and long chain (DEHP) phthalates. Mechanical shaking and
Cosmetic and personal care products were collected from centrifugation were also employed to aid the extraction process.
retail stores in Canada (see supplementary Technical Appendix) At the end of extraction, the upper clear organic solvent layer was
between December 2007 and April 2008. All standards and collected and diluted 10 times prior to instrumental analysis. After
organic solvents were from commercial sources (see supple- the first round of analysis, some extracts were further diluted to
mentary Technical Appendix). Deionized water (18.3 mO cm) an appropriate concentration and re-analyzed in order to make
was prepared using a Super-Q water generation system (Fisher the instrument response signal within the linear range of the
Scientific, Ottawa, Canada). All standard solutions and spiking calibration curve.
solutions were prepared in hexane. Method performance including recoveries was provided in
the supplementary Technical Appendix.
2.2. Sample preparation
2.3. Measurement of phthalates
Sample preparation was similar to that described elsewhere
(Wang et al., 2009) with some minor modifications. Briefly 0.4 g of Phthalates were determined by gas chromatography-mass
each sample was accurately weighed into a 15 mL vial using an spectrometry (GC–MS) using an Agilent gas chromatograph (Agi-
analytical balance. 40 mg of three internal standards, DMP-d4, DnBP- lent Technologies 6890 N Network GC System), coupled with an
d4, and DEHP-d4 were spiked into each sample and spiked samples Agilent mass selective detector (Agilent 5973 Network MSD).
were left standing overnight for equilibrium before solvent extraction. Phthalates were separated on a DB-5 MS column (30 m  0.25 mm
Different combinations of solvents were used for extracting phtha- I.D.  0.25 mm film thickness, J&W Scientific, Folsom, CA, USA). The
lates from products of different types in order to achieve good GC conditions were: injection port temperature, 280 1C; initial
332 D. Koniecki et al. / Environmental Research 111 (2011) 329–336

oven temperature, 45 1C for 5 min; initial ramp rate, 15 1C/min till deodorants (including antiperspirants) and lotions, respectively.
210 1C; second ramp rate, 8 1C/min to 270 1C; final ramp rate, Some of these products, three deodorants, one body lotion and
30 1C/min to 310 1C, and kept at 310 1C for 25 min. MSD was one body cream, contained DEP levels greater than 1000 mg/g.
operated in full scan mode. The ions used for quantifying the DEP was detected in 33 of the 98 (34% detection frequency) baby
phthalates were m/z 167 for DMP-d4, m/z 153 for DnBP-d4 and care products. In general, the levels of DEP in baby care products
DEHP-d4, m/z 163 for DMP, and m/z 149 for the remaining were below 1000 mg/g except for one diaper cream.
phthalates. The qualification of the phthalates was based on the While DEP was not detected in nail polish products, DnBP was
related mass spectrum of each compound extracted from the found in three of the 20 nail polish products at a concentration level
chromatograms. of 24,304, 22,947 and 3478 mg/g, respectively. Relatively high levels
of DEHP were also found in one nail polish (1045 mg/g) and two
2.4. Estimation parameters for dermal exposure fragrances (521 mg/g; 382 mg/g). DnBP and DEHP levels in other
products, if detected, were generally low at less than 40 mg/g. For
The exposure dosage calculation was based on the percentage the other two phthalates, DiBP was detected only at levels less than
of a topically applied dose that permeates the skin. The algorithm 10 mg/g and DMP was found in only one (deodorant) product at
(Eq. (1)) involved the concentrations of phthalates in products 72 mg/g.
(C, mg/g), the amount of product applied (AF, g/use), frequency of Dermal exposure from various types of cosmetic and personal
application (FD, time/d), retention factor (RF), percutaneous care products was estimated for three age groups of consumers:
absorption (A, %) and body weight (bw, kg). adolescent women, toddlers and infants (Table 5). Exposure
dosage was not calculated for phthalates which were detected
Exposure ðmg=kg bw=dÞ ¼ Cðmg=gÞ  AFðg=useÞ  FDðtime=dÞ at trace only (maximal value of 10 mg/g or less). The combined
RF  Að%Þ=bwðkgÞ ð1Þ maximal daily exposure dosage from use of all surveyed products
was calculated at 0.03, 78, 0.36 and 0.82 mg/kg bw/d for DMP,
Scenarios for the use of cosmetic and personal care products DEP, DnBP and DEHP, respectively, for an adolescent woman. The
including the amounts of products use per application (AF) and the maximal daily exposure to DEP for the two age groups, babies 0–6
frequency of use of products (FD) were based on data obtained from month old and toddlers from 0.5 to 4 years old was estimated at
several United States and European Union surveys (U.S. EPA, 2008; 42 and 20 mg/kg bw/d, respectively.
RIVM, 2006; Wormuth et al., 2006). The retention factor (RF) is a
default value to account for rinsing off and dilution of finished
products by application to wet skin or hair (Wormuth et al., 2006; 4. Discussion
SCCNFP, 2002). Assumptions made were that body weights of
female adolescent (20+ years), toddlers (0.5–4 years ), infants (0–6 4.1. Levels of phthalates in tested products
months) were 60, 15.5 and 7.5 kg, respectively (EC, 1998). A daily
exposure dosage can be estimated using these factors and the The results from this study confirmed findings of several earlier
concentrations in the products that were determined in this study. studies (SCCP, 2007; Hubinger and Harvey, 2006; Houlihan et al.,
For the present estimation, an absorption value (A) of 5% was used 2002) that DEP is the most frequently used phthalate in cosmetic
for all products except for nail polish (0.6%  2) (see the discussion and personal care products. DEP is used by industry as a fragrance
for the rationale supporting these values). component. The relatively high concentrations in the products and
high detection frequencies of DEP in this study reflect this industry
practice. The detection frequency of DnBP in nail products in this
3. Results study (3 out of 20 products, 15%), however, was much lower than
that reported in earlier studies. The detection frequency of 67% in
Among the 18 monitored phthalates (see supplementary nail polish products was reported by both Hubinger and Harvey
Technical Appendix), only five were detected in the products. (2006) and Houlihan et al. (2002), and up to 90.5% (19/21) by Koo
They are dimethyl phthalate (DMP), diethyl phthalate (DEP), and Lee (2004). DnBP has been banned for use in cosmetics includ-
diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP) and ing nail polishes in the European Union since 2004, but has still
di(2-ethylhexyl) phthalate (DEHP). Summary results of the levels been used in nail polishes in North America. The lower DnBP
of these five phthalates are provided in Table 4, which listed the detection frequency in our study might indicate a possible gradual
number of products in which at least one phthalate was detected, phase out of DnBP from nail polish formulations for products sold
the median value and maximal value of detected target phtha- in Canada.
lates in all samples of a particular subtype. The detection limits of Although DiBP was detected in some products, the highest
each of these five phthalates are also provided in Table 4. Detailed level of DiBP was 4.5 mg/g. This suggests that DiBP was present as
information on the levels of phthalate in each individual sample an impurity and was not intentionally added to cosmetic and
is given in the supplementary Technical Appendix. In all, 112 personal care products. Out of 252 products tested, except for the
samples were found to contain at least one phthalate at a three products that contained relatively high concentration of
detectable level. The detection frequencies of the five phthalates DEHP (521 and 382 mg/g in two fragrance products, and 1045 mg/
were in the following order: DEP (103 out of 252 pro- g in a nail polish), DEHP was only detected in trace levels, likely
ducts)4DnBP (15/252)4DiBP (9/252)4DEHP (8/252)4DMP being present as an impurity. This is consistent with the Govern-
(1/252). DEP was detected in almost all types of products (except ment of Canada’s proactive risk management measures which do
nail polishes). High DEP levels were largely concentrated in not permit the use of DEHP in cosmetics. DMP was only detected
fragrances. Of the 23 cosmetic and personal care products that in 1 of the 252 products at a concentration level of 72 mg/g.
had DEP levels greater than 1000 mg/g, 16 were fragrances, with In our analysis of 98 baby care products only DEP was
the highest value of 25,542 mg/g (equal to 2.6%). Although hair detected, except for one low level of DEHP in a baby lotion
care products had a similar detection frequency for DEP (70%) as (15 mg/g) and two low levels of DnBP (0.9 and 1.8 mg/g, respec-
that of fragrances, the DEP levels were much lower in hair care tively) in baby shampoos, which were likely present as impurities.
products with only one product having DEP level greater than There is no reason to believe therefore that DEHP and DnBP were
1000 mg/g. The detection frequency of DEP was 45% and 34% for intentionally formulated in baby products.
D. Koniecki et al. / Environmental Research 111 (2011) 329–336 333

Table 4
Phthalate concentrations (mg/g) in cosmetic and personal care products (Products that had non-detectable phthalates are not listed).

Product Type (n1) Subtype (n1) DMP DEP DiBP DnBP DEHP

Detection Limit 0.5 0.5 0.1 0.1 0.5


Fragrance (30) Fragrance (30) Detection 0 21 0 0 3
Median ND 1679 ND ND ND
Max ND 25542 ND ND 521

Hair care (24) Hair spray (11) Detection 0 8 1 2 1


Median ND 3.1 ND ND ND
Max ND 1223 1.1 36 1.6
Mousse (7) Detection 0 6 2 5 0
Median ND 19 ND 2.0 ND
Max ND 566 1.3 20 ND
Hair gel (6) Detection 0 3 0 0 0
Median ND ND ND ND ND
Max ND 445 ND ND ND

Deodorant (31) Deodorant (18) Detection 1 9 1 0 0


(excluding antiperspirant)
Median ND 3.7 ND ND ND
Max 72 3634 4.5 ND ND
Antiperspirant (13) Detection 0 5 0 0 0
Median ND ND ND ND ND
Max ND 818 ND ND ND

Nail polish (20) Nail polish (20) Detection 0 0 1 3 2


Median ND ND ND ND ND
Max ND ND 0.4 24304 1045

Lotion (29) Body lotion (20) Detection 0 7 1 0 0


Median ND ND ND ND ND
Max ND 5549 4.1 ND ND
Body cream (9) Detection 0 3 0 0 0
Median ND ND ND ND ND
Max ND 3444 ND ND ND

Skin cleanser (20) Skin cleanser (20) Detection 0 8 3.0 2 1


Median ND ND ND ND ND
Max ND 277 1.0 6.6 30

Baby product (98) Baby lotion (25) Detection 0 9 0 0 1


Median ND ND ND ND ND
Max ND 571 ND ND 15
Baby oil (19) Detection 0 5 0 0 0
Median ND ND ND ND ND
Max ND 15 ND ND ND
Diaper cream (31) Detection 0 5 0 0 0
Median ND ND ND ND ND
Max ND 2566 ND ND ND
Baby shampoo (23) Detection 0 15.0 0.0 2 0
Median ND 2.1 ND ND ND
Max ND 320 ND 1.8 ND

1–n: the total number of samples.


DMP ¼dimethyl phthalate, DEP ¼ diethyl phthalate, DiBP ¼ diisobutyl phthalate, DnBP ¼di-n-butyl phthalate, DEHP¼ di(2-ethylhexyl) phthalate.

With the amendment in 2006, the Canadian Food and Drugs Act model comparison of several phthalates (DEP, DMP, DnBP, and
and Cosmetic Regulations require that all ingredients be disclosed DEHP) (Scott et al., 1987), DEP was absorbed most extensively
on the label of cosmetic and personal care products. For fra- with a rate comparable to that of DMP (Table 6). The absorption
grances, however, a generic term ‘‘parfum’’ is only required. All through rat skin in vitro of neat DMP was 25.578.5% (Mint and
products tested in this study that contained DEP levels greater Hotchkiss, 1993) and about 35% of the applied dose at 72 h for
than 1000 mg/g had the generic description term as ‘‘parfum’’ DEP in ethanol (Elsisi et al., 1989). However, human skin is less
listed on their labels but no specific mentioning of DEP or other permeable to phthalates, with absorption values at about 5% for
phthalates on the label. Among the three nail polish products that DEP, 4% for DMP and about 0.5% for DnBP from various studies
contained DnBP levels greater than 1000 mg/g, two products did (Elsisi et al., 1989; Bronaugh et al., 1982; Scott et al., 1987; Mint
list DnBP on the product label. and Hotchkiss, 1993; Mint et al., 1994). For the purpose of
discussion, we used DEP % absorption through human skin (5%)
for all phthalates when calculating the daily exposure to support
4.2. Possible dermal exposure through use of cosmetics and personal the conservative approach in estimating exposure dosage (SCCP,
products 2007), except for nail polish products.
The information on subungual penetration rate for nail polish
Among various parameters in Eq. (1) for the estimation of products is rare. One study has reported a total subungual
dermal exposure, percutaneous absorption (A, %) is a parameter penetration of 8.5% over 14 days for neat DBP (Jackson, 2008).
that is not easy to determine and is highly variable (Azzi et al., In the absence of other relevant information, we assumed a constant
1995; Barber et al., 1992; Payan et al., 2001). Based on an in vitro penetration rate in this case and used a penetration of 0.6% per 24 h.
334 D. Koniecki et al. / Environmental Research 111 (2011) 329–336

Table 5
Estimation of daily dermal exposure dosage of Canadians in three different age groups to phthalates in cosmetic and personal care products.

Product type Product Frequency of Retention Exposure estimates (mg/kg bw/d)a


applied application factor
(g/use) (times/d)
DMP DEP DnBP DEHP

Max Median Max Max Max

Fragrance 0.61 3 1 2.6 39.0 0.8


Lotion 8 1 1 37.0
Hair care 5 1 0.1 0.5 0.015
Deodorant 0.5 1 1 0.030 1.5
Nail polish 0.25 0.28 1 0.34 0.01
Skin cleanser 2.5 2 0.1 0.12 0.01
Total (adult female)b 0.03 2.6 78 0.36 0.82

Baby lotion 1.4 0.14 1 0.37 0.01


Baby shampoo 0.51 0.27 0.01 0.001
Baby diaper cream 1.4 1.72 1 20
Baby oil 1.3 1.57 1 0.10
Total 0.5-4 yrsc 20 0.01

Baby lotion 1.4 0.14 1 0.75 0.02


Baby shampoo 0.51 0.27 0.01 0.003
Baby diaper cream 1.4 1.72 1 41
Baby oil 1.3 1.57 1 0.21
Total 0 -6 mo.d 42 0.02

DMP ¼dimethyl phthalate, DEP ¼ diethyl phthalate, DiBP ¼ diisobutyl phthalate, DnBP¼ di-n-butyl phthalate, DEHP¼ di(2-ethylhexyl) phthalate.
a
For concentrations see Table 4. Exposure was not estimated when phthalates were detected at traces (10 mg/g or less).
b
Assuming body weight (bw) of 60 kg (EC, 1998).
c
Assuming body weight of 15.5 kg (EC, 1998).
d
Assuming body weight of 7.5 kg (EC, 1998).

Table 6
Experimentally derived and model estimation of skin absorption and permeation of selected phthalate.

Chemical Rat skin Human skin Reference In Silicoa

Absorption Permeability Absorption Permeability Permeability


rate (mg/cm2/h) coefficient (cm/h) rate (mg/cm2/h) coefficient (cm/h) coefficient (cm/h)

DMP 41.6 7 4.18 34.50 7 3.51  10  5 3.957 0.64 3.32 70.54  10  5 Scott et al. (1987) 1.63  10  3
DEP 41.37 7 9.28 37.00 78.3  10  5 1.277 0.11 1.14 70.10  10  5 Scott et al. (1987) 4.19  10  3
DnBP 39.2 1.7 Mint and Hotchkiss (1993) 5.72  10  2
DnBP 9.337 0.09 8.95 7 0.09  10  5 0.077 0.02 0.23 70.06  10  5 Scott et al. (1987) 5.72  10  2
DEHP 2.247 0.23 2.28 7 0.23  10  5 1.067 0.23 0.57 70.12  10  5 Scott et al. (1987) NCb
DEHP 0.427 0.13  10  3 4.31 7 1.28  10  7 0.107 0.02  10  3 1.057 0.21  10  7 Barber et al. (1992) NCb

DMP ¼dimethyl phthalate; DEP ¼diethyl phthalate; DnBP ¼di-n-butyl phthalate; DEHP ¼ di(2-ethylhexyl) phthalate.
a
These permeability coefficients were not obtained from the cited references but were calculated with the NIOSH (2009) Skin Permeation Calculator available at
/www.cdc.gov/niosh/topics/skin/skinPermCalc.htmlS using the Potts and Guy (1992) model.
b
Not calculated (NC): since the Log Kow value of 7.6 for DEHP was outside range of dataset used by Potts and Guy (1992).

The resulting exposure dosage was multiplied by 2 to account for developmental status than is the general population. The Amer-
application of nail polish products to fingers and toes. ican Academy of Pediatrics published a study (Sathyanarayana
The parameters of consumer use patterns in Table 5 were et al., 2008) stating that infants are exposed to phthalates in
based on the existing consumer use patterns and were expected infants’ products including baby lotions, baby powder and baby
to represent conservative estimates (U.S. EPA, 2008; RIVM, 2006; shampoo. With respect to the third group, women are likely to
Wormuth et al., 2006). A more accurate reflection of real life use more cosmetic and personal care products than the male
consumer use patterns could be generated using a probabilistic population. Age-behavioral patterns of teenagers and adults are
modeling such as based on current consumer use patterns. But it similar (Wormuth et al., 2006).
would require a collection of large sample sizes of the market Only the fragrance products had sufficiently high detection
data on the consumer use pattern in Canada for the statistical frequency of DEP to produce a median value of DEP (1679 mg/g)
analysis. Although an exposure distribution in terms of quantity (Table 4). The median values for other phthalates in our study
and frequency of product used per day might be helpful in the were below the detection due to infrequent detection (Table 4).
assessment of human exposure, collection of large sample of The estimation of median dermal daily exposure of DEP (2.6 mg/
product users could be costly and time consuming, and the data kg bw/d) was similar to the mean exposure of 2.017 mg/kg bw/d
on products use might not be readily available. reported by Koo and Lee (2004) based on their measured levels of
Consumers are in dermal contact with various cosmetic and phthalates in cosmetic and personal care products and use data
personal care products on a daily basis. Babies and young children obtained from a questionnaire administered during the study. In
are vulnerable groups with respect to phthalates due to their our study, children’s exposure to DEP (42 and 20 mg/kg bw/d, for
D. Koniecki et al. / Environmental Research 111 (2011) 329–336 335

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