Heavy Metal Index
Ask the IndexAboutIndex Pro

Measurement of traces of heavy metals in cosmetic raw materials and finished products according to ISO/DIS 21392:2021 using triple quadrupole ICP-MS

Cite this pageVersion history

Overview

This Thermo Fisher Scientific application note (AN003602, January 2025) demonstrates a triple-quadrupole ICP-MS workflow on a Thermo Scientific iCAP MTX instrument for quantifying 19 trace elements in cosmetic products following ISO/DIS 21392:2021. Seventeen finished cosmetics from the French and European market and eight cosmetic raw materials were digested by microwave (Milestone ultraWAVE SRC) and analyzed in both KED and TQ-O₂ modes. The note’s primary contribution is methodological — showing that TQ-O₂ mode eliminates tungsten-on-mercury (¹⁸⁴W¹⁶O¹H⁺ on ²⁰¹Hg) and zirconium-on-cadmium (⁹⁴Zr¹⁶O¹H⁺ on ¹¹¹Cd) polyatomic interferences that KED mode cannot fully suppress — but it also reports concentrations for seven aggregated finished-product categories and ten raw materials, useful as occurrence context.

Key numbers

  • Study design: 27 samples total — 17 finished products + 10 raw materials (the paper’s narrative says “eight” raw materials, but Tables 2 and 6 enumerate ten; the ten-row tabulation is treated as authoritative). Sample preparation per ISO/DIS 21392:2021: 200 mg sample digested with 1 mL H₂O + 5 mL HNO₃ + 1 mL HCl, digestate transferred to 50 mL with ultrapure water then 4× further dilution to 200 mL final volume in 2.5% HNO₃ / 0.5% HCl; total dilution factor ×1000 (p. 3 Table 3; p. 2 narrative).
  • Method quantification limits (MQL, mg·kg⁻¹), Table 4 (p. 4): Pb 0.004, Cd 0.010, As 0.031, Hg 0.017, Cr 0.041, Ni 0.115, Sb 0.010, Al 1.118, Sn 0.047, Co 0.002, Tl 0.002, Se 0.718, Be ≤0.001, Mn 0.005, Fe 0.149, Zn 0.232, Ti 1.169, Pt 0.023, W 0.101.
  • Acquisition mode: Pb, Co, Ni, Sn, Sb, Be, Al, Fe, Tl, Pt, W used SQ-KED; Cr, Mn, As, Se, Cd, Zn, Ti, Hg used TQ-O₂ with on-mass measurement after O₂ reaction (Table 4 p. 4).
  • EU regulatory ceilings cited (Regulation EC 1223/2009, p. 2): Cr 10, Pb 10, As 5, Cd 5, Hg 1 mg·kg⁻¹.
  • Finished-product concentrations (Table 5, p. 5), reported as the range across samples in each aggregated category, mg·kg⁻¹:
  • Nail varnish (3 varnish samples): Pb 0.17-0.64; Cd <MQL-0.01; As <MQL; Hg <MQL; Cr 0.17-0.29; Ni 0.12-0.20; Sb <MQL-0.02; Sn 0.02-0.25; Al 667-1,079; Ti 10.4-364; Fe 256-352; Mn 1.09-49.6; Zn 11.5-46.4; Co 0.04-0.06.
  • Balm and lipstick (lip balm + 1 other solid lip product, n unstated for the category): Pb <MQL-0.86; Cd <MQL-0.04; As <MQL-0.09; Hg <MQL; Cr 0.01-0.37; Ni 0.01-0.33; Sb <MQL-0.08; Sn 0.01-18.1; Al <MQL-311; Ti 0.01-332; Fe 0.01-138; Mn 0.01-5.01; Zn <MQL-54.8; Co 0.01-0.09.
  • Perfumes (perfume mist, hair perfume, eau de cologne, solid perfume, perfume, eau de toilette, eau de parfum): Pb 0.01-5.59; Cd <MQL; As <MQL; Hg <MQL; Cr <MQL-21.6; Ni <MQL-20.5; Sb <MQL-0.01; Sn <MQL-0.23; Al 0.08-33.0; Ti <MQL-6.44; Fe <MQL-89.4; Mn 0.01-2.14; Zn 0.03-76.8; Co <MQL-0.39.
  • Toothpaste (n=1): Pb 0.85; Cd <MQL; As <MQL; Hg <MQL; Cr 0.65; Ni <MQL; Sb <MQL; Sn 0.77; Al 31.6; Ti 4.77; Fe 15.0; Mn 0.26; Zn 27.1; Co 0.04.
  • Micellar water (n=1): Pb 0.17; Cd <MQL; As <MQL; Hg <MQL; Cr <MQL; Ni <MQL; Sb <MQL; Sn <MQL; Al <MQL; Ti 0.55; Fe <MQL; Mn 0.07; Zn 11.0; Co <MQL.
  • Cream and gel (scrub cream, hand cream, pink clay mask, exfoliating cleansing gel): Pb 0.27-2.30; Cd <MQL; As <MQL; Hg <MQL; Cr <MQL-8.00; Ni <MQL; Sb <MQL; Sn <MQL-0.67; Al <MQL-11,344; Ti 1.62-308; Fe <MQL-955; Mn 0.02-3.80; Zn 13.2-1,677; Co <MQL-0.37.
  • Nourishing body milk (n=1): Pb 0.19; Cd <MQL; As <MQL; Hg <MQL; Cr <MQL; Ni <MQL; Sb <MQL; Sn <MQL; Al <MQL; Ti 1.42; Fe <MQL; Mn 0.03; Zn 16.3; Co <MQL.
  • Notable finished-product highs: perfume Pb max 5.59 mg·kg⁻¹ (within EU 10 mg·kg⁻¹ ceiling); cream/gel Al max 11,344 mg·kg⁻¹ and Zn max 1,677 mg·kg⁻¹ (no EU ceiling for either); perfume Cr max 21.6 mg·kg⁻¹ (above the EU 10 mg·kg⁻¹ ceiling); perfume Ni max 20.5 mg·kg⁻¹; balm/lipstick Sn max 18.1 mg·kg⁻¹.
  • Raw-material concentrations (Table 6, p. 5), mg·kg⁻¹ unless noted as % w/w; digestion incomplete for 9 of 10 raw materials (Ophiopogon japonicus root the only complete digestion):
  • Iron oxide mica: Pb 4.63; Cd <MQL; As 0.21; Hg <MQL; Cr 8.18; Ni 11.3; Sb 0.16; Sn 56.0; Al 5.8% (w/w); Ti 258; Fe 18.0% (w/w); Mn 165; Zn 97.9; Co 3.37; W 14.0; Be 6.58; Tl 1.58.
  • Titanium dioxide (anastase form): Pb 0.66; Cd <MQL; As <MQL; Hg <MQL; Cr <MQL; Ni 0.11; Al 14.1; Ti 212; Fe 15.6; Mn 0.07; Zn 0.93.
  • Iron oxide mica / aluminum oxide blend: Pb 5.51; Cd <MQL; As 0.14; Hg <MQL; Cr 5.84; Ni 2.69; Sn 21.8; Al 5.2% (w/w); Ti 196; Fe 16.8% (w/w); Mn 28.4; Zn 15.8; Co 3.09; W 10.9; Be 3.74; Tl 0.55.
  • Hollow silica sphere: Pb 2.78; Cd <MQL; As <MQL; Hg <MQL; Cr 0.28; Ni 0.26; Al 6.17; Ti 2.71; Fe 17.8; Mn 0.17; Zn 42.8; Sb 0.03.
  • Ophiopogon japonicus root extract (complete digestion): Pb 0.05; Cd 0.04; As 0.62; Hg <MQL; Cr 0.14; Ni 0.32; Al 23.8; Ti 0.63; Fe 11.5; Mn 17.2; Zn 5.12; Co 0.08; Sb 0.02.
  • White powder A: Pb 4.20; Cd <MQL; As 0.09; Hg <MQL; Cr 3.50; Ni 1.95; Al 8.68; Ti 194; Fe 26.2; Mn 0.60; Zn 24.9; Co 0.26; Sn 0.05.
  • White powder B: Pb 4.08; Cd <MQL; As <MQL; Hg <MQL; Cr 5.01; Ni 2.63; Al 7.00; Ti 180; Fe 36.2; Mn 0.78; Zn 22.8; Co 0.12.
  • Titanium dioxide (rutile form): Pb 2.26; Cd <MQL; As <MQL; Hg <MQL; Cr 0.50; Ni 0.15; Al 0.1% (w/w); Ti 246; Fe 7.90; Mn 1.23; Zn 32.8; Pt 0.11.
  • Titanium dioxide / iron oxide / silica blend: Pb 4.35; Cd <MQL; As <MQL; Hg <MQL; Cr 15.7; Ni 17.8; Sn 160.8; Al 3.2% (w/w); Ti 249; Fe 10.7% (w/w); Mn 376; Zn 39.8; Co 5.12; Be 0.82; Tl 0.27.
  • Mica pellets coated with iron and titanium: Pb 5.96; Cd <MQL; As <MQL; Hg <MQL; Cr 3.04; Ni 4.62; Sn 5.02; Al 1.8% (w/w); Ti 422; Fe 19.4% (w/w); Mn 851; Zn 36.0; Co 3.94; Be 0.64; Tl 0.19.
  • Tungsten-on-mercury interference demonstration (Table 8, p. 6): in iron oxide mica (W = 14.0 mg·kg⁻¹) KED-mode ²⁰¹Hg = 33.48 mg·kg⁻¹ but TQ-O₂ mode <0.017 mg·kg⁻¹ (the MQL); in iron/aluminum oxide (W = 10.9 mg·kg⁻¹) KED-mode ²⁰¹Hg = 31.49 mg·kg⁻¹ but TQ-O₂ <0.017 mg·kg⁻¹. The KED-mode values exceed the EU 1 mg·kg⁻¹ Hg ceiling by ~30×; TQ-O₂ reveals no Hg is actually present.
  • Zirconium-on-cadmium interference demonstration (Figure 6, p. 8): zero added Zr → ¹¹¹Cd KED 0; +1 µg·g⁻¹ Zr → ¹¹¹Cd KED 0.54 µg·g⁻¹ (false positive), TQ-O₂ ~0; +10 µg·g⁻¹ Zr → ¹¹¹Cd KED 5.20 µg·g⁻¹ (false positive), TQ-O₂ 0.06 µg·g⁻¹.
  • Spike recovery (Figure 7, p. 9): per-element recovery across 16 finished-product matrices ranged 60-105% for the seven measured isotopes (⁵²Cr, ⁵⁹Co, ⁶⁰Ni, ⁷⁵As, ¹¹¹Cd, ¹²¹Sb, ²⁰⁸Pb); the source narrative claims all within the 70-150% ISO/DIS 21392:2021 acceptance window, but the data table shows three sub-70% values on a single sample, Hair perfume (⁵²Cr 67%, ⁵⁹Co 69%, ⁶⁰Ni 60%); all other 15 samples are within the 70% floor for all seven isotopes.
  • Internal standard stability over >120 samples / >8 h: 80-110% recovery for all five internal standards (⁷³Ge, ¹⁰³Rh, ¹¹⁵In, ¹⁷⁵Lu, ¹⁹³Ir) in both KED and TQ-O₂ modes (Figure 1, p. 4), well within the 70-130% ISO/DIS 21392:2021 robustness window.

Methods (brief)

Instrument: Thermo Scientific iCAP MTX triple-quadrupole ICP-MS with iSC-65 autosampler, iCAP MX Series Nebulizer, Ni-tipped sample and skimmer cones, PLUS torch, cyclonic quartz spray chamber. Operated with Argon Gas Dilution (AGD level-5, ~5× automatic dilution) to manage variable total dissolved solids across cosmetic matrices. Two acquisition modes: SQ-KED (collision, helium 4.91 mL·min⁻¹) and TQ-O₂ (reaction, 0.31 mL·min⁻¹) on the same run. RF power 1,550 W; 3 replicates per sample (Table 1, p. 2).

Sample preparation per ISO/DIS 21392:2021: microwave-assisted acid digestion (Milestone ultraWAVE Single Reaction Chamber system); reagents dispensed by Milestone EasyFILL (1 mL H₂O + 5 mL HNO₃ + 1 mL HCl per 200 mg sample); 200 °C plateau for 30 min. Note that complete digestion was not achieved for 9 of 10 raw materials (silica/mica/oxide deposits persisted); for those samples the reported concentrations represent the acid-leachable fraction rather than total elemental content. Digestate diluted to 50 mL with ultrapure water, then 4× further dilution and 0.45 µm membrane filtration before injection. Internal standards (¹⁰³Rh for Cr/Co/Ni/As/Cd/Sb; ¹⁷⁵Lu for Pb per the ISO standard, plus ⁷³Ge/¹¹⁵In/¹⁹³Ir added by the authors for robustness check) introduced online at 1,000 µg·L⁻¹ before nebulization.

Speciation discipline: 75As measured as ⁷⁵As¹⁶O⁺ product ion in TQ-O₂ — this is total arsenic, no inorganic/organic speciation performed (recorded as tAs). Mercury measured on ²⁰¹Hg in TQ-O₂ mode — this is total mercury, no methylmercury speciation (recorded as tHg). Chromium measured on ⁵²Cr¹⁶O⁺ product ion — this is total chromium, no Cr-VI / Cr-III separation (recorded as Cr). Tin measured on ¹¹⁸Sn in SQ-KED — total tin, no organotin speciation (recorded as Sn).

Calibration: standards 0.5-10 µg·L⁻¹ in matched acid matrix (2.5% HNO₃ / 0.5% HCl) for trace elements; up to 2,500 µg·L⁻¹ for the high-concentration elements (Al, Ti, Fe). R² ≥0.9964 for all 19 analytes (W is the lowest at R² 0.9964; Be is 0.9986; Al, Ti, Zn, Sn at R² >0.9999; the rest fall between; Table 4 p. 4). Accuracy validated by spike-recovery on the 16 finished-product matrices (Figure 7, p. 9). LOD and MQL reported in Table 4.

Limitations: (1) Sample selection is convenience, not representative — 25 samples drawn from the authors’ lab to demonstrate workflow; not designed as an occurrence survey. (2) Incomplete digestion for raw materials means raw-material values are minimum estimates of total content. (3) Speciation is absent for As, Hg, Cr, Sn. (4) The note is a vendor publication promoting Thermo Scientific instruments; reported figures of merit reflect the demonstration laboratory’s optimized conditions.

Implications

  • Certification (HMTc): Method-validation reference for the ISO/DIS 21392:2021 analytical approach now widely adopted in cosmetic regulatory labs. The demonstration that KED-mode Hg in tungsten-containing raw materials produces >30× false-positive concentrations is operationally important — labs relying on KED-only quadrupole ICP-MS for cosmetics analysis may be over-reporting Hg in mica- and tungsten-bearing finished products. Auditors of Children's Makeup (ages 0-5), Children's Nail Polish (ages 0-5), Makeup — foundation, powders, blush/rouge, and other mica-pigment-using product categories should ask whether the lab used reaction-cell mode for Hg. The reported finished-product concentrations (Table 5) are occurrence context only, not population-level evidence (n=1 per category for toothpaste, micellar water, body milk; n=17 total across all categories).
  • Courses: Useful methods-module reading for a cosmetic-QA / analytical-chemistry course unit on triple-quadrupole ICP-MS interference removal, particularly for instructors covering W/Mo/Zr-based polyatomic interferences on Hg and Cd.
  • App: Not relevant to ingredient contamination_profile (cosmetics are not in the food-ingredient taxonomy).

Update history

No substantive edit history is available in this build. The full commit record is available in git.

Referenced by