Survey of cosmetics for arsenic, cadmium, chromium, cobalt, lead, mercury, and nickel content

Overview

This U.S. Food and Drug Administration analytical survey, published in J. Cosmet. Sci., reports total-content measurements of seven inorganic elements (As, Cd, Cr, Co, Pb, Hg, Ni) in 150 cosmetic products spanning 12 product types purchased on the U.S. market in spring/summer 2011. The contract analytical work was conducted at Frontier Global Sciences (Bothell, WA) under FDA contract. The methodology used closed-vessel microwave-style oven HNO₃/HF/HCl digestion at 130 °C for 12 h (modified from the lipstick method validated in FDA’s 2007 and 2010 lipstick surveys), ICP-MS for As/Cd/Cr/Co/Pb/Ni, and cold-vapor atomic fluorescence spectrometry (CVAFS) for Hg. The paper is the FDA’s broad-survey companion to its earlier 20-lipstick (2009) and 400-lipstick (2012) Pb-only surveys, extending the analyte panel to seven elements and the product scope from lipsticks alone to 12 cosmetic product types.

Key numbers

All values are total-content concentrations in mg/kg (= ppm = µg/g) of finished cosmetic product as placed on market; mean and median are computed across the per-product replicate-mean values within each product-type group, with <LOD (NF) values set to zero and <LOQ but >LOD (TR) values included at the numerical mid-range reported. The 95th-percentile column in Table XXIX is computed across the full n=150 dataset. Where the source provides a parenthesised value (column “(value)”), that is the same statistic recomputed after Grubbs outlier exclusion at p = 0.05.

Limits of detection and quantitation (Table II, p. 126)

LODs were calculated as three times the standard deviation, and LOQs as ten times the standard deviation, of ten replicate reagent blanks fortified with low-level standards.

Per-product-type summary statistics (Tables XVII-XXVIII)

Mean and median across the per-product replicate-mean values within each product-type group, in mg/kg. Values in parentheses are the same statistic recomputed after Grubbs outlier exclusion (p = 0.05) where the source reports an outlier-removed companion value.

NF = Not Found, i.e. result below the LOD for that element. TR = Trace, i.e. result between LOD and LOQ; summary statistics in the source set <LOD values to zero and include TR values at their numerical mid-range, per the source’s stated convention (Survey of Cosmetic Samples paragraph, p. 141).

All cosmetic categories combined (Table XXIX, p. 142; n = 150)

Outlier-excluded companion values in parentheses where the source reports them.

The maximum-cell entries in Table XXIX correspond to individual outlier samples whose attributes are described in the Discussion (pp. 141-143): one face-paint sample contained 15000 mg/kg chromium, and the 22,000 mg/kg Cr in one eye shadow is attributed to chromium-pigment use (“chromium oxide greens” or “chromium hydroxide greens”); the 1,600 mg/kg Ni and 64 mg/kg Co in one eye shadow were identified by Grubbs test (p = 0.05) as outliers and were rejected from category-summary t-tests; a qualitative X-ray fluorescence scan of the eye-shadow holder did not detect Co or Ni, suggesting the cosmetic itself (and not the container) was the source of the metals.

Regulatory comparison points reported by the source

The Discussion notes (p. 143) that “FDA limits the level of mercury to less than 1 ppm (1 mg/kg) in most cosmetics and none of the products examined exceeded that limit.” The U.S. regulatory framework discussed (p. 125): U.S. regulations under 21 CFR §73, 74, 82, and 700.13 specify limits for elemental contaminants in color additives used in cosmetics, but there are no limiting specifications for these contaminants in cosmetics themselves, with mercury being the one exception. The paper does not propose new thresholds or compare its findings to other-jurisdiction limits.

Methods (brief)

Sampling and sample selection. 150 cosmetic samples purchased between April 22, 2011 and August 16, 2011 by Frontier Global Sciences (Bothell, WA) according to a detailed list provided by FDA: 30 eye shadows, 30 blushes, 30 lipsticks, 15 lotions (5 medium-and-low priced, 5 premium/high priced, 5 with sunscreen), 10 mascaras, 10 foundations, 5 body powders, 5 compact powders, 5 shaving creams, 10 face paints. FDA developed the product list with primary emphasis on market share. Powder products and face paints were selected from individual web sites to span high-, medium-, and low-priced and niche items.

Sample digestion (Sample Digestion Procedure, pp. 135-137). 0.5 ± 0.1 g of analytical portion transferred to a 60 mL Teflon digestion vessel (Savillex 100% high purity). 25 mL of 3:1 HNO₃:HF mixture plus 3 mL of HCl added. Vessels sealed and heated in an oven at 130 °C for 12 h. Solutions then transferred to centrifuge tubes and diluted to 50 mL. For mercury analyses, a 4 mL aliquot was transferred to a separate tube and diluted to 40 mL with 5% (v/v) bromine monochloride. For ICP-MS analytes, the original digest was transferred to Teflon beakers, heated on a hot plate at ≤200 °C until volume reduced to 2-3 mL, then 25 mL of concentrated HNO₃ was added and the evaporation repeated three further times (so HF was largely eliminated and no boric-acid neutralisation was applied — distinguishing this method from prior lipstick methods that added boric acid to redissolve precipitated metal fluorides). Two method blanks were included in each digestion batch of ≤20 samples. One organic oil reference material (Conostan for non-mercury metals, SPEX for mercury) and one inorganic reference material (NIST 2702) were included in each digestion batch. Each sample was prepared in duplicate.

ICP-MS determination of As, Cd, Cr, Co, Pb, Ni (pp. 137-138). Perkin Elmer Nexion 300X ICP-MS. Isotopes used for quantitation (bolded in source list): ⁵³Cr, ⁶⁰Ni, ⁷⁵As, ⁵⁹Co, ¹¹¹·¹¹⁴Cd, ²⁰⁶·²⁰⁷·²⁰⁸Pb (sum of three Pb isotopes used to account for isotopic variation between samples and standards). Internal standards: ⁴⁵Sc, ¹¹⁵In, ¹⁹⁵Pt. Initial calibration with 8 calibration standards (Table I, p. 126); continuing calibration verification (CCV) standards analysed every 15 analytical solutions. Standard-curve correlation coefficient > 0.997 in all cases; CCV recoveries within 90-110%. Samples analysed with a 1/10 dilution of the diluting solution (1% HNO₃ + 0.5% HCl v/v). Absence of matrix effects verified by comparing one analytical solution from each digestion batch with the same solution at a 1/20 dilution; relative percent differences (RPDs) < 20%. Method-blank QC: analytical solutions with values above the highest standard were additionally diluted to bring them on-curve.

CVAFS determination of Hg (pp. 138-139). Tekran 2600 mercury cold vapor gold-amalgamation atomic fluorescence spectrometer. Mercury was analysed prior to the evaporation steps used to prepare samples for ICP-MS (to avoid loss of Hg through volatilisation). Solutions were first oxidised (1% v/v bromine monochloride solution prepared from 1.5% potassium bromide and 1.1% potassium bromate in concentrated HCl) to ensure all Hg was in a stabilised oxidation state, then treated with hydroxylamine hydrochloride (25% w/v in 1% HCl) to neutralise remaining oxidant, then reduced with stannous chloride (25% w/v in 15% HCl) through an online mixing system to form volatile elemental Hg vapour. A gas-liquid separator removed the Hg vapour, which was deposited on a gold bed through amalgamation; the gold bed was then heated to release the Hg vapour, carried by argon gas into the atomic fluorescence spectrometer at 253.7 nm. Calibration: blank plus 5 calibration standards (0.5, 1, 5, 2, 40 ng/kg) prepared daily from dilution of the primary stock standard (1000 mg/kg, High Purity Standards). CCV recoveries within 90-110%. QC reference materials: NIST 1641e (mercury in water).

Reference materials and recovery (Tables III and IV, pp. 127-128). Four matrix-matched reference materials were analysed: Conostan custom oil (1 µg/g As, Pb, Cd; 5 µg/g Cr, Co, Ni — no certified Hg), Spex custom oil (5 µg/g Hg), NIST 695 trace elements in multi-nutrient fertilizer, NIST 2702 inorganics in marine sediment, NIST 1573a tomato leaves. Recovery limits 70-130% for certified values < 10× the LOQ; 90-110% for certified values ≥ 10× the LOQ. Reported mean recoveries (Table IV): Conostan 93-106% across the seven elements; NIST 695 96-102%; NIST 2702 90-104%; NIST 1573a 90-96% (Pb not certified for NIST 1573a). One exception: Hg recovery from Spex custom oil ran 71-79% across triplicate weight tests (0.25, 0.50, 0.75 g) — lower than the 75-104% Hg recoveries on the inorganic and biological matrices. The authors note the cause is not understood and report the values uncorrected.

Speciation: total content only for all metals. ICP-MS without speciation chromatography; CVAFS quantifies total mercury after BrCl oxidation to convert all Hg species to Hg(II). This paper’s As enters the wiki as tAs (not iAs), Hg as tHg (not MeHg), Cr as Cr (not Cr-VI) — the underlying measurements do not separate inorganic from organic species or oxidation states.

Implications

• Certification (HMTc). This paper contributes A-tier total-content occurrence data on the U.S. cosmetic market for seven of the HMTc-relevant elements (Pb, Cr, Ni, tAs, Cd, tHg, Co; Co is not on the HMTc 10-analyte panel per Part 14 but is in scope for category-fitness questions). Direct-evidence data are available for HMTc Cat 13 (Cosmetics and Personal Care — Leave-on) Rows 5 (foundation/powders/blush), 7 (eye makeup), and 10 (sun/suntan products); HMTc Cat 14 (Rinse-off) Row 7 (shaving cream/gel/foam); HMTc Cat 2 Row 12 (children’s face paint, to the extent the FDA’s “face paints” category includes products marketed to or used by children — the paper does not separate kids’ vs adult costume face paints). Per-product-type median values in the table above are the direct inputs HMTc would pool against literature-baseline percentiles in the Standards Workbench. The 22,000 mg/kg Cr, 1,600 mg/kg Ni, and 64 mg/kg Co outliers are pigment-based product-design choices (chromium-oxide green pigment, nickel/cobalt-rich mineral pigments) and would be relevant to a clean/dirty subcategory split if HMTc were considering pigment-based formulations as a separate subrow. The outliers were rejected by the authors’ Grubbs test for category-mean statistics but they are real measured values on real U.S.-market products and should not be silently dropped during HMTc pooling.
• Courses. Useful as a teaching case for (a) the FDA’s regulatory posture on cosmetic elemental contaminants (no limiting specifications for the cosmetic itself except Hg; limits only on color additives via 21 CFR §73/74/82), (b) the inadequacy of acid-only digestion (without HF) when cosmetic samples contain refractory mineral pigments such as titanium dioxide and mica — the paper’s modification of the prior lipstick method to add HF and remove boric-acid neutralisation is the methodological pivot, and (c) the use of isotope-sum quantitation (Pb at ²⁰⁶+²⁰⁷+²⁰⁸) to handle isotopic variation between cosmetic samples and calibration standards.
• App. Not directly relevant to ingredient contamination_profile (the paper does not measure metals in cosmetic ingredients individually). The product-type-level medians and 95th-percentiles are however a useful prior for any future app feature that estimates contamination likelihood in cosmetic product categories from product type alone.
• Microbiome: not addressed.

Related evidence

• Lead
• Cadmium
• Arsenic, Total
• Mercury, Total
• Chromium
• Nickel
• Cobalt
• Eye makeup (liners, shadows, mascara, brow products, false lash adhesives, lash/eyebrow serums)
• Makeup — foundation, powders, blush/rouge
• Lip products (lipstick, gloss, lip liner, adult lip balm)
• Body/hand leave-on skin care
• Sun/suntan products (including spray, self-tan, airbrush)
• Dusting/talc powders (adult)
• Shaving cream/gel/foam
• Face Paint

Update history

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