4.6 6.

Review

Recent Advances in Sample

Preparation for Cosmetics and
Personal Care Products Analysis

Maria Celeiro, Carmen Garcia-Jares, Maria Llompart and Marta Lores

Special Issue
Last Advances in Cosmetics and Personal Care Products Analysis
Edited by
Dr. Maria Celeiro and Prof. Dr. Maria Llompart

https://doi.org/10.3390/molecules26164900
 molecules
Review
Recent Advances in Sample Preparation for Cosmetics and
Personal Care Products Analysis
Maria Celeiro 1, * , Carmen Garcia-Jares 1 , Maria Llompart 1 and Marta Lores 2

1 CRETUS Institute, Department of Analytical Chemistry, Nutrition and Food Science,

Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain;
[email protected] (C.G.-J.); [email protected] (M.L.)
2 Laboratory of Research and Development of Analytical Solutions (LIDSA),
Department of Analytical Chemistry, Nutrition and Food Science, Universidade de Santiago de Compostela,
E-15782 Santiago de Compostela, Spain; [email protected]
* Correspondence: [email protected]; Tel.: +34-8818-14464

Abstract: The use of cosmetics and personal care products is increasing worldwide. Their high
matrix complexity, together with the wide range of products currently marketed under different
forms imply a challenge for their analysis, most of them requiring a sample pre-treatment step before
analysis. Classical sample preparation methodologies involve large amounts of organic solvents as
well as multiple steps resulting in large time consumption. Therefore, in recent years, the trends
have been moved towards the development of simple, sustainable, and environmentally friendly
methodologies in two ways: (i) the miniaturization of conventional procedures allowing a reduction
in the consumption of solvents and reagents; and (ii) the development and application of sorbent-
and liquid-based microextraction technologies to obtain a high analyte enrichment, avoiding or





 significantly reducing the use of organic solvents. This review provides an overview of analytical
methodology during the last ten years, placing special emphasis on sample preparation to analyse
Citation: Celeiro, M.;
Garcia-Jares, C.; Llompart, M.;
cosmetics and personal care products. The use of liquid–liquid and solid–liquid extraction (LLE, SLE),
Lores, M. Recent Advances in Sample ultrasound-assisted extraction (UAE), solid-phase extraction (SPE), pressurized liquid extraction
Preparation for Cosmetics and (PLE), matrix solid-phase extraction (MSPD), and liquid- and sorbent-based microextraction tech-
Personal Care Products Analysis. niques will be reviewed. The most recent advances and future trends including the development of
Molecules 2021, 26, 4900. https:// new materials and green solvents will be also addressed.
doi.org/10.3390/molecules26164900
Keywords: sample preparation; microextraction techniques; miniaturization; cosmetics; personal
Academic Editor: Toshio Morikawa care products

Received: 30 July 2021

Accepted: 11 August 2021
Published: 13 August 2021
1. Introduction

Publisher’s Note: MDPI stays neutral

The use of cosmetics and personal care products is increasing worldwide, and Europe
with regard to jurisdictional claims in
is a key market for the cosmetics industry. In fact, the European cosmetic market generated
published maps and institutional affil-
more than EUR 120,000 billion in 2019 [1].
iations. Regulation 1223/2009 [2] includes the definition of cosmetics and establishes rules
to be complied with by any cosmetic product made placed on the market, to ‘ensure the
functioning of the internal market and a high level of protection of human health’. For
this purpose, it provides a ‘List of substances prohibited in cosmetic products’ (Annex II)
which currently includes more than 1400 chemical compounds. On the other hand, Annex
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
III lists the substances allowed for use as cosmetic ingredients, although most of them
This article is an open access article
present restrictions in terms of maximum permitted concentration depending on the use of
distributed under the terms and
the final product or the product type. In addition, different positive lists of substances for
conditions of the Creative Commons several ingredient families, such as colorants, preservatives, and UV filters (Annexes IV, V
Attribution (CC BY) license (https:// and VI, respectively) are included [2,3]. It is important to note that although Regulation
creativecommons.org/licenses/by/ 1223/2009 came into force in 2013, it is continuously revised and updated (with more than
4.0/). 60 amendments since it came into effect).

Molecules 2021, 26, 4900. https://doi.org/10.3390/molecules26164900 https://www.mdpi.com/journal/molecules

Molecules 2021, 26, 4900 2 of 31

From the point of view of their composition, cosmetics are very complex, with variable
matrices formed by a high number of substances from highly lipophilic to moderately
polar, or exhibiting basic, acidic, or neutral properties. In addition, it is quite frequent that
technical mixtures containing impurities or unknown or banned/unexpected compounds
that can be formed by the reaction of compounds become present in the formulation under
particular exposition conditions [4,5].
Taking into account that cosmetic products marketed on the European Union must
comply with the Regulation [2], and that this compliance must be analytically verifiable,
the analysis of cosmetics and personal care products is a challenge. A previous sample
pre-treatment before analytical determination is usually required. Sample pre-treatment
has two objectives: to ensure the pre-concentration of the target analytes as well as to
minimize analysis matrix effects.
In recent years, several reviews covering this topic have been published [3,5–11], most
of them focused on specific types of cosmetics ingredients such as fragrances, preservatives
or dyes since they are the most common compounds present in the formulations [3,9,10].
Regarding the reported sample preparation methodology for cosmetics analysis, traditional
liquid–liquid extraction (LLE) and solid–liquid extraction (SLE) are still employed, although
the use of advanced techniques such as ultrasound-assisted extraction (UAE), solid phase
extraction (SPE), matrix solid-phase dispersion (MSPD) or pressurized liquid extraction
(PLE) [3,4,6,7,12] is growing. In recent years, green analytical chemistry (GAC) principles
have been increasingly implemented for cosmetics analysis through the miniaturization
of classical extraction procedures, as well as the substitution of hazardous chemicals and
solvents by environmentally friendly alternatives, as the main objective is to improve their
environmental friendliness without compromising method performance [13–15].
The separation and determination of the target analytes in the cosmetics matrices are
mainly performed by gas chromatography (GC) and liquid chromatography (LC). The
choice between them depends on the chemical nature of the target analytes. In general, LC
is the preferred option for the most polar compounds such as preservatives or UV filters,
especially for hydroxyl preservatives or benzophenone-UV filters derivatives. On the other
hand, GC is the preferred chromatographic technique for the separation of volatile or
semi-volatile compounds such as fragrances, although non-polar compounds (UV filters,
preservatives, etc.) are also successfully analysed by GC. In this case, a derivatization step
is included during the sample pre-treatment to modify several chemical functions of the
original low-volatile compounds. Derivatization usually employs acetylation with acetic
anhydride, or silyl derivatives to improve the chromatographic peak shape of the most
polar compounds. This step is usually performed in situ during the extraction step to
obtain a good method performance in a short amount of time.
Due to the capability of several compounds present in cosmetics, such as UV filters or
some plasticizers, to absorb light in the UV-Vis spectrum, diode-array detector (DAD) was
the preferred detection method after LC separation. However, due to its low specificity,
which complicates quantifying multiple compounds in complex sample matrices, such as
cosmetics, the combination of GC or LC with mass spectrometry (MS) or tandem mass
spectrometry (MS/MS) detection became the most suitable option. This approach improves
the analytical selectivity and sensibility, allowing the detection of the target analytes at trace
levels, which is especially important to identify the impurities and banned compounds.
In recent years, the use of high-resolution mass spectrometry (HRMS), mainly based on
QTOF detection, has started to play a more important role for multitarget analysis.
The main objective of this review is to provide an update on the cosmetics and personal
care products’ sample preparation methodology. The most relevant analytical methods
reported (Scopus database) in the last decade (2010–2020) for the extraction and determina-
tion of organic compounds, including cosmetics ingredients such as UV filters, fragrances,
preservatives, plasticizers or dyes, as well as the strategies to determine impurities, banned
or unexpected compounds (N-nitrosamines, polycyclic aromatic hydrocarbons (PAHs),
pesticides, antibiotics, etc.) will be presented. The application of both traditional sample
Molecules 2021, 26, 4900 3 of 31

preparation based on direct dilution, LLE or SLE as well as advanced techniques such
as ultrasound-assisted extraction (UAE), solid-phase extraction (SPE), pressurized liquid
extraction (PLE), matrix solid-phase extraction (MSPD) to cosmetics matrices will be ad-
dressed. The recent trends in liquid- and sorbent-based microextraction techniques will
be also discussed. Figure 1 illustrates the sample preparation strategies included in this
review. The novel developments regarding miniaturization, new sorbent materials with
high adsorption properties and the most recent technological trends will also be addressed.

Figure 1. Sample preparation techniques for cosmetics analysis included in this review.

2. Sample Preparation Strategies for Cosmetics Analysis

Traditional cosmetics sample preparation techniques involve liquid–liquid extraction
(LLE) and solid–liquid extraction (SLE). However, the main drawback of SLE and LLE is
their high organic solvent (hundreds of mL) and time consumption. On the other hand,
modern sample extraction techniques are advancing towards fast sample processing, easy
automatization, as well as a reduction in organic solvent volumes, in agreement with
the green chemistry principles [13]. In this way, ultrasound-assisted extraction (UAE),
solid-phase extraction (SPE), pressurized liquid extraction (PLE) and matrix solid-phase
dispersion (MSPD) are techniques that can be considered environmentally friendly, as most
of them easily miniaturized [14,16,17]. The most relevant analytical methodologies based
on these techniques are summarized in Table 1 and commented on below.

2.1. Direct Sample Dilution

Direct dilution (or ready-to-inject) is still employed as a suitable option for simple
formulations such as perfumes or liquid cosmetics, but it is not adequate for complex
matrices and formulations such as most of the currently marketed cosmetics and personal
care products, where a high number of compounds at different concentrations coexist.
In addition, from a practical point of view, this approach can negatively affect the chro-
matographic system. Direct dilution was successfully employed for the determination
of phthalates [18,19] and for the simultaneous analysis of fragrance allergens, synthetic
musks, phthalates and preservatives [20] from perfumes and simple liquid cosmetic matri-
ces. Ethanol [18,19] or ethyl acetate [20] were the most employed dilution solvents, used in
volumes ranging between 1 and 10 mL. For multianalyte determination, the sample:solvent
volume ratio was a critical parameter since target compounds can be present at very differ-
ent concentration levels. In these cases, different dilutions, between 1:10 v/v and 1:1000 v/v
can be required [20]. Analyses were directly performed by gas chromatography–mass spec-
trometry (GC-MS) for perfumes, whereas an additional evaporation and reconstitution step
was required for the other cosmetics matrices [18]. In all cases, satisfactory performance in
terms of recovery (between 80 and 128%) and precision was achieved.
Molecules 2021, 26, 4900 4 of 31

2.2. Liquid–Liquid and Solid–Liquid Extraction (LLE, SLE)

LLE and SLE are two of the oldest sample preparation techniques for cosmetics
analysis due to their ease of use and low-cost materials [5,6]. To obtain the highest extraction
efficiency in LLE, the extraction solvent should not be miscible with the matrix eluent to
solubilize the maximum of analytes. In SLE, extraction is similar to LLE, however, in this
case, analytes are dispersed in a solid matrix [21]. SLE and LLE were applied to extract
a broad range of organic compounds, including allowed cosmetic ingredients such as
preservatives (parabens, isothiazolinones, triclosan, etc.), antioxidants, adipates, UV filters
and dyes, as well as banned compounds such as nonylphenols, phthalates, or bisphenol-
and dioxane derivatives, among others [22–30]. The most critical experimental parameter
in LLE and SLE is the extraction solvent. Its selection depends on the target analyte or
the analytes’ properties and on the determination technique. Solvents from intermediate
polarity (MTBE [22,23,27], acetonitrile [28], mixture of solvents [29]) to more polar ones
(MeOH [25,26], EtOH [30], mixture EtOH/water [24]) have been employed. The solvent
volume ranged between 1.5 mL and 50 mL and multiple extraction steps were required in
some cases to obtain an optimum extraction yield. LLE and SLE procedures were usually
assisted by stirring, mechanical shaking, or vortex agitation [22,24,25,27–29] to facilitate the
analytes’ transfer between the matrix and the solvent. However, one of the main drawbacks
of these techniques is the fact that after extraction, further steps such as the centrifugation,
concentration and reconstitution of the supernatant or SPE are usually conducted [22–27]
to obtain clean extracts before analytical determination.
Molecules 2021, 26, 4900 5 of 31

Table 1. Classical and advanced sample preparation strategies for cosmetics analysis: direct dilution, LLE, SLE, UAE, SPE, PLE and, MSPD.

Extraction
Sample Sample Extraction Extraction/Elution Post-Extraction Recovery RSD
Analytes Matrix Time Analysis LOD (ng mL−1 ) Ref.
Amount Pre-Treatment Technique Solvent Treatment (%) (%)
(min)
Direct dilution
10 mL EtOH Other cosmetics:
LOQ: 1000
Perfumes, shampoos, 1 mL Direct dilution (perfumes), 10 mL centrifugation, drying
Dilution in 10 mL (perfumes),
8 phthalates creams, body milks, (perfumes), (perfumes), H2 O + 10 mL (Na2 SO4 ), GC-MS >80 <10 [18]
H2 O (other cosmetics) 200 ng g−1
shower gels 1 g (others) SLE (others) MTBE (others reconstitution:
(cosmetics)
samples) 1mL EtOH
8 phthalates Perfumes 0.8 mL Direct dilution 0.8 mL EtOH GC-MS 88–128 3–294 <6 [19]
Fragrances,
Dilution (1:10,
synthetic musks,
Perfumes, colognes 0.1 mL Direct dilution 1:100 or 1:1000, GC-MS 89–110 <6 [20]
plasticizers,
v/v) EtAc
preservatives
Liquid–Liquid Extraction (LLE), Solid–Liquid Extraction (SLE)
Centrifugation,
Toothpastes, shampoos,
concentration,
hair conditioners, gels,
Alkylphenols, reconstitution in 3 mL
facial cleansers, hand LC-
bisphenols, 0.2–0.5 g SLE 5 mL MTBE 30 DCM/hexane (1:9, 66–135 LOQ: 0.2–1 ng g−1 [22]
soaps, sanitary products, MS/MS
preservatives v/v). SPE, elution: 10
lotions, creams,
mL DCM/EtAc (1:1,
makeup, lipsticks
v:v), concentration
Concentration,
Toothpastes, shampoos, evaporation,
face cleansers, bath gels, reconstitution: 3 mL
hand sanitizers, DCM/hexane (1:9, LC-
Bisphenols 0.2 g SLE 5 mL MTBE 20 91–113 1.4–85 ng g−1 [23]
sunscreens, body lotions, v/v). MS/MS
lipsticks, hand lotions, hair SPE, elution: 10 mL
gels, masks DCM/EtAc,
concentration
EtOH/H2 O (1:1, 0.5 (vortex Centrifugation,
4 phenols Cosmetics SLE, LLE LC-MS 90–116 7–15 <8 [24]
v/v), agitation) filtration
Lipsticks, lotions, creams,
8 preservatives, Mixture with 100 mg 5 (vortex LC-
masks, shampoos, gels, 0.1 g SLE 1.5 mL MeOH Filtration, dilution MP 70–117 LOQ: 600–3400 ng g−1 <16 [25]
14 dyes C18 agitation) MS/MS
soaps, gels, toothpastes
Dilution in
6 plasticizers, 7 UHPLC-
Shower gels 0.1 g LLE 5 mL MeOH MeOH/H2 O (75:25, 96–105 490–2600 ng g−1 <12 [26]
preservatives MS
v/v)
Shampoos, body washes, Centrifugation,
2 preservatives, 30 LC-
face cleansers, lipsticks, 0.2 g SLE 5 mL MTBE evaporation until 1 mL, 5–20 ng g−1 [27]
2 phthalates (shaking) MS/MS
hair dyes filtration
25 mL ACN + 25
mL MeOH/H2 O 15 Centrifugation, HPLC-
12 preservatives Creams, gels, lotions 2g SLE 95–105 <3 [28]
(1:1, v/v, 0.6% (shaking) filtration DAD
oxalic acid)
Molecules 2021, 26, 4900 6 of 31

Table 1. Cont.

Extraction
Sample Sample Extraction Extraction/Elution Post-Extraction Recovery RSD
Analytes Matrix Time Analysis LOD (ng mL−1 ) Ref.
Amount Pre-Treatment Technique Solvent Treatment (%) (%)
(min)
2 mL
Rinse-off, leave-on 3 (vortex GC-
1,4-dioxane 0.2 g LLE, SLE hexane/DCM Centrifugation, SPE 84–108 200 ng g−1 <4 [29]
cosmetics agitation) MS/MS
(80:20, v/v)
Sunscreen, creams, balms, HPLC-
15 UV filters 0.01–0.02 g SLE 10 mL EtOH Filtration 97–104 30–220 <8 [30]
after shaves UV
Ultrasound-Assisted Extraction (UAE)
Dilution with 4 mL Centrifugation,
THF (0.2% 6 mL MeOH/H2 O evaporation, LC-
15 UV filters Sunscreens 0.1 g UAE 10 87–104 2000–20,000 ng g−1 <8 [31]
ammonium (80:20, v/v) reconstitution: 1 mL MS/MS
hydroxide), vortex MeOH, filtration
Lipsticks, foundations, 5 mL
Centrifugation, LC-
9 preservatives deodorants, lotions, soaps, 0.1 g UAE MeOH/ACN (1:1, 10 900–4200 [32]
filtration MS/MS
toothpastes v/v),
Hydroxyethoxy-
Creams, sunscreens,
phenyl 0.1 g UAE 10 mL H2 O Filtration LC-UV 86–103 30,000 ng g−1 <5 [33]
shampoos, soaps, make-up
butanone
Tonics, creams, lotions,
6 preservatives 1g UAE 6 mL MeOH 15 Dilution, filtration LC-DAD 69–119 150–5300 <11 [34]
shower gels, masks
Perfumes, shampoos,
15 synthetic lotions, soaps, Concentration to
0.03 g UAE 3 mL (×2) hexane 20 GC-MS 83–94 0.12–20 ng g−1 [35]
musks antiperspirants, 0.2 mL
sunscreens
50 µL NaCl (aq) +
ε-aminocaproic 950 µL 0.2 mol
UAE (40 KHz, HPLC-
acid + amino Cosmetics 0.02 g L−1 borate buffer + 10 Dilution, filtration 77–122 0.09–0.15 <4 [36]
40 ◦ C) FL
acids 80 µL of
100 mM NBD
Gels, shampoos, creams,
HPLC-
2 plants derived antioxidant ampoules, 0.4 g UAE 25 mL EtOH 1 Filtration, dilution 93–115 18–13 µg g−1 <9 [37]
UV
lotions, masks
4 natural HPLC-
Temporary tattoos 0.02–0.03 g UAE (35 kHz) 7.5 mL MeOH 5 Filtration 100–200 <2 [38]
pigments DAD
A
wipe/mask,
20 mL (wipes),
70 compounds: 0.1 g
Masks, baby wipes, 2 mL (cosmetics),
fragrances, (cosmetics), UAE (50 KHz,
extreme cosmetics, UAE, sup-UAE 5 mL (products 10 Dilution, filtration GC-MS 70–120 <10 [39]
preservatives, 0.05 g 25 ◦ C)
borderline products with applicators)
plasticizers (products
EtAc
with
applicators)
Molecules 2021, 26, 4900 7 of 31

Table 1. Cont.

Extraction
Sample Sample Extraction Extraction/Elution Post-Extraction Recovery RSD
Analytes Matrix Time Analysis LOD (ng mL−1 ) Ref.
Amount Pre-Treatment Technique Solvent Treatment (%) (%)
(min)
Dilution in 20 mL
6 µmol TB+ (0.4
2-propanol (0.1%, w/v
Free UAE-CPE mg L−1 sulphite, Dilution to 1.2 mL
Hair cosmetics 0.5–1 g SDS), UAE, 15 UV-Vis 95 0.38 <5 [40]
formaldehyde (50 ◦ C) 0.05% Triton EtOH
centrifugation + 2 mL
X-114)
EtOH, dilution
Depilatory wax strips, HPLC-
500 µL CAN + 200
liquid foundations, DAD,
2 resin acids 0.05 g UCSED (60 ◦ C) µL of ANITS 45 Filtration 95–104 8–24 <3 [41]
mascaras, eyeliner, online
solution
lip balms MS/MS
Dilution in 10 mL
ACN/H2 O (2%
Evaporation,
formic acid, 1:2, v/v),
1 mL (×2) MeOH: reconstitution: 1 mL
shaking, UAE, SPE (Oasis
ammonium MeOH/ACN: H2 O (5 LC-
16 antibiotics Anti-acne samples 0.5 g centrifugation, MCX® 3 cc/60 81–113 0.5–1.6 ng g−1 <12 [42]
hydroxide (4:1, mM ammonium MS/MS
evaporation, mg cartridge)
v/v) formate), 12:88, v/v,
reconstitution with
filtration
2 mL H2 O
(0.1% formic acid)
Dilution in 10 mL
MeOH/H2 O (1:9,
v/v), vortex, UAE, Evaporation,
SPE (Oasis
22 coumarin Creams, lotions, centrifugation, 4 mL MeOH/H2 O reconstitution: 2 mL LC-
1g HLB® 80–93 LOQ: 5–20 ng g−1 <15 [43]
derivatives shampoos, lipsticks evaporation, (1:9, v/v) ACN/H2 O MS/MS
cartridge)
reconstitution with (70:30, v/v), filtration
2 mL MeOH/H2 O
(1:9, v/v)
Dilution in 10 mL
0.5 g (water H2 O (water soluble
soluble products), 2 mL H2 O
products), + 8 mL DCM (soaps), SPE (Bond Elut
LC-
NDELA Soaps, emulsions 0.1 g (soaps), 2 mL H2 O + 4.5 mL AccuCAT® 1 mL H2 O 91–114 1 <15 [44]
MS/MS
0.25 g (water H2 O + 10 chloroform, cartridge)
insoluble (water insoluble
products) products),
centrifugation
Creams, make-up, lotions, Dilution (dil Evaporation,
SPE (20 mg HPLC-C-
4 parabens shampoos, after 1g 1:20–1:100) in H2 O, 2 mL acetone reconstitution: 0.5 mL 82–104 500–2100 <8 [45]
MWCNTs) CAD
sun lotions UAE, centrifugation mobile phase
Dilution in 3 mL NaCl
(aq) + 10 mL ACN + Evaporation,
0.2 mL potassium SPE (MIP- reconstitution: 1 mL HPLC-
Prednisone Creams 0.5 g 3 mL (×3) MeOH 83–106 5 <2 [46]
ferrocyanide (aq) + MWCNTs) ACN/H2 O (40:60, v/v), UV
0.2 mL zinc acetate, filtration
UAE, centrifugation
Molecules 2021, 26, 4900 8 of 31

Table 1. Cont.

Extraction
Sample Sample Extraction Extraction/Elution Post-Extraction Recovery RSD
Analytes Matrix Time Analysis LOD (ng mL−1 ) Ref.
Amount Pre-Treatment Technique Solvent Treatment (%) (%)
(min)
Dilution in 10 mL Evaporation,
NaOH (0.001 M) SPE (MIP: reconstitution:
Shampoos, HPLC-
BPA 0.025 g + 10 mL ethylether, imprinted 1 mL MeOH MeOH/H2 O (65:35, 87–97 0.001 micromol L−1 <9 [47]
bath lotions, creams UV/FL
centrifugation silica NPs) v/v)
+ 10 mL toluene
Dilution in 5 mL
6 benzotriazole Lotions, emulsions, SPE (GS HPLC-
1g MeOH, UAE, 0.8 mL acetone 89–105 0.03–0.10 <8 [48]
UV filters creams, sunscreens cartridge) UV
filtration
Dilution in 5 mL
SPE 2.5 mL Evaporation,
7 0.1 M
Anti-acne samples 0.2 g (CGO/PVC MeOH:acetone, reconstitution: IC-UV 88–102 3.4–7.1 <6 [49]
sulphonamides acetate-ammonium
cartridge) (6:5, v/v) 0.5 mL MP
(aq), vortex, UAE
Dilution in H2 O or SPE (Ni-Zn-
PABA Creams, sunscreens 0.1 g 2.5 mL NaCl (2M) UV 96–101 3.7 <4 [50]
EtOH Al(NO3 − )LDH)
Dilution in 3 mL NaCl
(aq), vortex + 2 mL
ACN. Centrifugation
+ 2 mL ACN + 10 mL
0.1 mL ACN/H2 O
9 H2 O +
Cosmetics samples 0.2 g SPE-PMME (80:20, v/v, 0.3% LC-MS 84–104 0.1–1.9 <15 [51]
glucocorticoids K4 [Fe(CN)6 ]·3H2 O
formic acid)
(10%, w/w) + zinc
acetate (20%, w/w).
Centrifugation,
filtration
Evaporation,
Dilution in 7 mL dSPE-MWCNT reconstitution: 1 mL
11 LC-
Skin care products 1g ACN, vortex, UAE, (50 mg 3 MeOH/formic acid (aq, 89–128 7–250 ng g−1 <30 [52]
N-nitrosamines MS/MS
centrifugation MWCNT-10) 0.1%) (3:7, v/v),
filtration
Dilution in 1 mL Filtration, evaporation,
VA-d-SPE-
MeOH, stirring, reconstitution: 500 µL HPLC-
7 parabens Creams 0.5 g MOF (150 mg 2 mL MeOH 5 64–121 0.1–0.6 <12 [53]
centrifugation. of ACN/H2 O (35:65, DAD
HKUST-1)
Dilution in H2 O v/v)
Dilution in 3 mL
MeOH, UAE + 50 mL d-SPE (SBA-
Sunscreen, antiperspirants, 500 µL MeOH (3% HPLC-
3 preservatives 0.05 g H2 O. Filtration 15/PANI-p- 40 82–108 0.1–0.4 <7 [54]
creams, lotions v/v acetic acid) UV
+ 500 mL with TSA-NCs)
acetate buffer
Pressurized Liquid Extraction (PLE)
20 mL
Mixture with Na2 SO4 LC-
15 UV filters Sunscreens, cosmetics 0.1 g PLE (90 ◦ C) MeOH/acetone 10 Dilution in MP 82–101 LOQ: <100 ng g−1 <12 [55]
+ 0.6 g sand MS/MS
(1:1, v/v)
Molecules 2021, 26, 4900 9 of 31

Table 1. Cont.

Extraction
Sample Sample Extraction Extraction/Elution Post-Extraction Recovery RSD
Analytes Matrix Time Analysis LOD (ng mL−1 ) Ref.
Amount Pre-Treatment Technique Solvent Treatment (%) (%)
(min)
Sunscreens, hair products, Mixture with 0.6 g Dilution in EtAc, GC-
15 UV filters 0.1 g PLE (90 ◦ C) 10 mL ACN 10 >80 <10 [56]
nail polishes, lipsticks Florisil® derivatization MS/MS
Moisturizing creams, Mixture with 2 g 15 mL
26 fragrance
lotions, sunscreens, 1g PLE (120 ◦ C) hexane/acetone 15 GC-MS 85–114 12–1800 ng g-1 <10 [57]
allergens
aftersun lotions Na2 SO4 + 2 g Florisil® (1:1, v/v)

Mixture with 1 g PLE (120 ◦ C +

15 mL EtAc (1:1,
13 preservatives Leave-on cosmetics 0.5 g in situ GC-MS 74–110 40–1000 ng g−1 <10 [58]
Na2 SO4 + 1 g Florisil® derivatization)
v/v)

Evaporation + 500 mL
H2 O, SPE, evaporation, LC-
PFOS, PFOA Waterproof sunscreen 4–5 g PLE (80 ◦ C) 60 mL MeOH 30 67–102 <20 [59]
reconstitution: MS/MS
0.5 mL MP
26 fragrance
allergens, 13
Baby wipes, wet toilet Individual Dilution in EtAc,
preservatives, PLE (110 ◦ C) 20 mL MeOH 5 GC-MS 75–119 1-31 ng g−1 <10 [60]
paper for children wipe filtration
15 phthalates, 11
musks
25 fragrance Mixture with 1 g 20 mL
allergens, 13 Baby, child cosmetics 0.5 g PLE (120 ◦ C) hexane/acetone 15 Derivatization GC-MS <12 [61]
preservatives Na2 SO4 + 2 g Florisil® (1:1, v/v)
Matrix solid-phase dispersion (MSPD)
Creams, lotions, MSPD (2 g 5 mL
25 fragrance Dilution (1:10, v/v or
shampoos, gels, 0.5 g hexane/acetone GC-MS 75–118 20–600 ng g−1 <5 [62]
allergens
conditioners, soaps Florisil® ) (1:1, v/v)
1:1000, v/v)

Body milks, lipsticks,

MSPD (2 g 5 mL
creams, sunscreens,
13 preservatives 0.5 g hexane/acetone Derivatization, dilution GC-MS 88–110 1.4–39 ng g−1 <4 [63]
deodorants, shampoos, Florisil® ) (1:1, v/v)
soaps
Dilution in
Shampoos, cleansing gels, MSPD (2 g H2 O/MeOH (0.1%
LC-
4 preservatives baby bath gels, creams, 0.5 g 5 mL MeOH formic acid, 5 mM 60–80 LOQ: 6.6-60 ng g−1 <11 [64]
make-up Florisil® ) ammonium formate
MS/MS
(70:30, v/v))
Shampoos, soaps, body
18 plasticizers, milks, sunscreens, creams, µ-MSPD (0.4 g
0.1 g 1 mL EtAc GC-MS 84–105 1.4–300 ng g−1 <10 [65]
12 musks aftershave lotions, Florisil® )
deodorants
Molecules 2021, 26, 4900 10 of 31

Table 1. Cont.

Extraction
Sample Sample Extraction Extraction/Elution Post-Extraction Recovery RSD
Analytes Matrix Time Analysis LOD (ng mL−1 ) Ref.
Amount Pre-Treatment Technique Solvent Treatment (%) (%)
(min)
26 fragrance
allergens, 15
Sunscreen, hair products, µ-MSPD (0.4 g
plasticizers, 11 GC-
creams, make-up, lip 0.1 g 1 mL ACN Dilution, filtration 97–111 <10 [72]
synthetic musks,
balms, make-up, lipsticks Florisil® ) MS/MS
13 preservatives,
14 UV filters
26 fragrance
allergens, 13 Gels, shampoos, soaps, µ-MSPD (0.4 g
preservatives, sunscreen, lotions, body 0.1 g 1 mL EtAc Dilution GC-MS 80–110 3–700 ng g−1 <15 [73]
15 plasticizers, milks, creams, deodorants Florisil® )
12 musks
13 PAHs, 13
pesticides, 8
Dilution 1:10, v/v in
phthalates, 10 µ-MSPD (0.4 g 1 mL EtAc GC-MS,
EtAc (GC–MS) or 1:5,
nitrosamines, 2 Hand creams, shower gels 0.1 g (GC-MS), ACN LC- 72–116 0.09–1.30 ng g−1 <15 [74]
dyes, 5 Florisil® ) (LC-MS/MS)
v/v in ACN/H2 O;
MS/MS
50:50, v/v), filtration
fragrances, 6
APEOs
Dilution in 0.3 mL MSPD (2 g
2 5 mL MeOH:acetic HPLC-
0.2 g MeOH: H2 O (1:19, 85–89 200–300 ng g−1 <6 [75]
glucocorticoids
v/v) + 0.1 g MMIM Florisil® ) acid (6:1, v/v) UV

ACN: acetonitrile; C-CAD: corona-charged aerosol detector; CGO/PVC: carboxylated graphene oxide/polyvinyl chloride; CPE: cloud point extraction; DAD: diode array detector; d-SPE: dispersive solid-phase
extraction; EtAc: ethyl acetate; EtOH: ethanol; FL: fluorescence detector; GC: gas chromatography; GS: graphene sponge; HPLC: high-performance liquid chromatography; IC: ion chromatography; LDH: layered
double hydroxide; LOD: limit of detection; LOQ: limit of quantification; MeOH: methanol; MP: mobile phase; MS: mass spectrometry; MTBE: methyl-tert-butylether; MWCNTs: multi-walled carbon nanotubes;
NBD-F: 4- fluoro-7-nitro-2,1,3-benzoxadiazole; RSD: relative standard deviation; SBA-15/PANI-p-TSA-NCs: polyaniline para-toluenesulfonic acid nanocomposite supported; SDS: sodium lauryl sulphate; THF:
tetrahydrofuran; UCSED: ultrasonic-assisted closed in-syringe extraction and derivatization; UHPLC: ultra-high-performance liquid chromatography; UV: ultraviolet; VA: vortex-assisted.
Molecules 2021, 26, 4900 11 of 31

2.3. Ultrasound-Assisted Extraction (UAE)

The fundament of UAE is based on the cavitation phenomena [76]: the creation of
small bubbles in the solvent due to the passage of ultrasound waves allowing for a greater
penetration of the solvent within the material, thus increasing the surface area. From a GAC
point of view, UAE is greener than classical LLE or SLE [77]. The inclusion of ultrasound
energy assisting solvent extraction allows the use of less solvents, reducing the extraction
time, costs, and improving the extraction yield.
UAE has been applied to cosmetics to extract UV filters, preservatives, synthetic
musks, amino acids, or natural pigments [31–38] from a broad range of matrices including
leave-on and rinse-off cosmetics, as well as specific products such as tattoos. The most used
solvents for UAE have been water [31,33], MeOH [34,38], EtOH [37], or the combination of
different organic solvents [32] or water before LC analysis, whereas hexane and ethyl acetate
have been the preferred ones before GC analysis [35,39]. For amino acids analysis, an in
situ derivatization was implemented, employing 4-fluoro-7-nitro-2,1,3-benzoxadiazole
(NBD-F) [36]. In all cases, quantitative recoveries, and low values for relative standard
deviation (RSD) and LODs were obtained.
Additionally, UAE has been successfully proposed for the multianalyte determination
of 70 compounds including fragrances, plasticizers and preservatives in baby wipes, masks
as well as in extreme cosmetics and borderline products [39]. The possible transfer of
plasticizers from the plastic applicators to the cosmetics matrices, and thereby to the
consumers, were evaluated, employing a modified version of the classical UAE, called
supported-UAE (Sup-UAE). In this approach, a small amount of cosmetic sample (0.05 g)
was applied with its corresponding applicator on a small piece (3 × 2.4 cm2 ) of filter paper
sheet. Sup-UAE performance was compared with µ-MSPD and classical UAE, obtaining
similar results in terms of recovery and precision, demonstrating its suitability, and giving
additional information about plasticizers’ migration from cosmetics applicators [39].
The use of UAE combined with cloud-point extraction (CPE) is a simple, low-cost,
and sustainable option. It reduces solvent consumption and extraction time, providing
high analyte enrichment factors. UAE-CPE has been applied for the extraction of free
formaldehyde from hair products [40]. Determination was performed by UV-Vis, obtaining
a LOD lower than 0.4 µg L−1 . The use of ultrasonic-assisted closed in-syringe extraction
and derivatization (UCSED) was performed for the determination of two labile resin
acids [41]. The procedure included in situ derivatization with 2-(2-(anthracen-10-yl)-1H-
naphtho[2,3-d]imidazol-1-yl)ethyl-p-toluenesulfonate (ANITS) and the analysis of HPLC-
DAD, and online MS/MS to ensure the confirmation of the target analytes presence in
a broad range of cosmetics matrices. In general, UAE performance in terms of accuracy,
precision and LODs was similar to that LLE or SLE (see Table 1). However, after UAE, no
further clean-up steps before analysis were necessary, reducing the extraction time, whereas
after LLE or SLE, a clean-up step, mainly by SPE, is usually implemented [22,23,29].

2.4. Solid Phase Extraction (SPE)

SPE is one of the most popular techniques for the extraction of organic compounds
from aqueous matrices. SPE allows the isolation of the target analytes from the sample to
a solid phase where they are retained. Afterwards, analytes are recovered by elution in
a solvent [78]. However, its application to cosmetics analysis usually requires a previous
sample pre-treatment, mainly performed by simple dilution in water [42,45,50] or an
organic solvent such as MeOH to obtain a liquid phase [43,46]. Undoubtedly, the sorbent
selection is critical to obtain a successful SPE method since it plays an important role in the
efficiency and analyte selectivity. In recent years, great efforts have been devoted to the
development, characterization and application of advanced sorbents to improve analyte
selectivity and specificity, with a high sorptive capacity, simultaneously enhancing their
physicochemical stability [79,80].
Nowadays, a wide range of existing commercial SPE sorbents are based on classical
normal phases (silica, alumina), reversed-phases (C18, C8) and ion exchange sorbents [80].
Molecules 2021, 26, 4900 12 of 31

The commercial reversed-phase water-wettable polymer N-vinylpyrrolidone-DVB

sorbent, commonly known as Oasis HLB® , presents a hydrophilic–lipophilic balance, thus
it can be used for acidic, basic and neutral analytes. Oasis HLB® has been employed to
extract coumarin derivatives from cosmetics [43]. Analysis was performed by LC–MS/MS,
obtaining recoveries between 80 and 93% and LODs lower than 20 ng g−1 . Another com-
mercially available mixed-mode cation-exchange reverse phase sorbent, known as Oasis
MCX® , a sulphonic-acid modified cross-linked polystyrene, has been employed for antibi-
otics determination in cosmetics [42]. The Bond Elut AccuCAT® cartridge, consisting of a
strong cation exchange (SCX), a strong anion exchange (SAX) and C18 was employed for
the isolation of the n-nitrosamine NDELA from cosmetics as well as from triethanolamine
(TEA), a commonly used cosmetic raw material frequently contaminated with NDELA.
This commercial sorbent showed the highest sensitivity and recovery with the least matrix
interferences [44]. The selection of the elution solvent is also a critical parameter. It depends
on the analyte properties and on the determination technique. Since several of the target
compounds are relatively polar, the use of polar solvents such as water [44] or mixtures of
water/methanol [42,43] has mainly been employed. In most cases, after SPE, evaporation
and reconstitution in the mobile phase composition was carried out to concentrate the
extracted analytes before LC-MS/MS analysis [42,43].

New Sorbent Materials for SPE

In recent years, new trends in SPE are closely related to the improvement of sorbents
that can be more effective to obtain higher analyte enrichment efficiency. These new
materials include carbon nanotubes (CNTs), graphene-sponge (GS) and graphene-oxide
(GO)-based materials, layered double hydroxides (LDHs) and metal organic frameworks
(MOFs)—among others. Their applications as SPE sorbents for cosmetics analysis are
presented below.
Carbon nanotubes (CNTs) were introduced by S. Iijima in 1991 [81]. CNTs are cylindri-
cal nanostructures composed of single or multiple rolled graphene sheets. The hollow fibres
have a diameter of 1–50 nm with length in the range of microns. They can be classified into
single walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs),
depending on the number of graphene sheets [82]. MWCNTs have attracted great atten-
tion for their specific characteristics to increase sensitivity, improving enrichment and
extract clean-up [80]. The combination of SPE with MWCNTs has been proposed to extract
parabens from cosmetics prior to corona-charged aerosol detection (C-CAD) [45]. Another
advantage of using MWCNTs is the fact that their surface can be functionalized, thus
enhancing their sorption performance and selectivity. In this way, the functionalization of
MWCNTs with a molecularly imprinted polymer (MIP) is an option that has been employed
for the determination of the corticosteroid prednisone in cosmetics [46]. This combination
allowed a reduction in the extraction time, and the sorbent material could be reused up to
four times without losing extraction efficiency, representing a suitable option for specific
analyte extractions in complex matrices. The use of MIPs has also been reported to extract
bisphenol A from leave-on and rinse-off cosmetics [47]. The analytical performance was
compared with those obtained employing classical C18 sorbents, showing that the use of
imprinted silica nanoparticles allowed higher specific extraction, with less interference.
Another recently developed nanomaterials employed as SPE sorbent for cosmetics analysis
is graphene sponge (GS). This material presents special characteristics such as negligible
weight, open-hole structure, high surface area and variable surface chemistry [83]. It has
been employed to extract benzotriazole UV filters from water and cosmetics [48]. The
sorbent efficiency was compared with the use of MWCNTs and C18. Results revealed that
GS showed the best extraction efficiency for the target compounds, which is attributed
to hydrogen bonding, π–π stacking and hydrophobic interactions between GS and the
benzotriazoles. In addition, the large surface area and pore size of GS probably enhance
the extraction capability. Another graphene-based sorbent that exhibits a large surface
area, chemical stability and durability is graphene oxide (GO). Its adsorption capacity can
Molecules 2021, 26, 4900 13 of 31

be attributed to the delocalized π-electron system, and its properties can be improved by
chemicals modifications such as the carboxylation of hydroxyl and epoxy groups on the GO
surface, greatly improving its extraction selectivity. In this way, the use of carboxylated GO
with polyvinyl chloride (CGO/PVC) was proposed to determine different sulphonamides
as contaminants in cosmetics’ products followed by IC-UV analysis [49]. A novel mono-
lithic capillary column with embedded graphene was developed and used for polymer
monolith microextraction (PMME). The monolith capillary contained poly butyl methyl
acrylate-ethylene dimethylacrylate-graphene (BMA-EDMA-GN) and it was successfully
applied for the extraction of nine glucocorticoids from cosmetics. High enrichment capacity
was observed in the case of a GN-entrapped monolith showing satisfactory reusability and
stability during extraction [51].
Other nano-structured materials gaining special attention in recent years for their
special physicochemical properties include layered double hydroxides (LDHs). These
are synthetic 2-dimensional nano-structured inorganic materials with general formula:
M2+ 1−x M3+ x (OH)2 ]x+ [An− x/n ·mH2 O]x− , where M2+ is a divalent metal ion (Zn, Mg, Cu,
Co or Ni), M3+ is a trivalent metal (Al, Fe or Cr), x is the ratio of M3+ /(M2+ + M3+ ) and An−
is a n-valent anion. A large variety of materials can be obtaining by varying the proportion
of the divalent and trivalent cations [84]. The use of a nickel-zinc-aluminium layered
double hydroxide (Ni-Zn-Al LDH) was assessed to extract the UV filter p-aminobenzoic
acid (PABA) from sunscreens [50]. Results showed quantitative recovery values, a high
repeatability and matrix independence even at the low concentration levels showing the
suitability of this nano-structured composite.
SPE on-column is the most employed mode [42–50], although the on-batch mode
has also been reportedly employed. Dispersive (d)-SPE is an alternative approach to
conventional SPE. In d-SPE, the sorbent is dispersed into the sample. The close contact
between the sorbent particles and the analytes greatly favours the sorption, increasing
the efficiency of the whole procedure. Finally, the extracted analytes are eluted from the
sorbent [85]. The use of MWCNTs in dispersive (d)-SPE has been proposed to determine
volatile-N-nitrosamines in skin care cosmetics [52]. After extraction, the MWCNTs were
removed before LC-MS/MS analysis. Analytical performance showed good recoveries and
precision, although LODs were quite high compared to those obtained for nitrosamines
employing µ-MSPD-GC-MS/MS analysis [74]. The use of nanocomposites as well as metal-
organic frameworks (MOFs) is increasing as SPE sorbents in d-SPE applications. MOFs
have emerged as new crystalline porous materials with promising applications. They
are hybrid inorganic–organic microporous crystalline materials self-assembled straight-
forwardly from metal ions with organic linkers via coordination bonds. MOFs present
interesting characteristics such as a high surface area, uniform structure cavities and a
permanent nanoscale porosity, among others. Moreover, the availability of various building
blocks of metal ions and organic linkers makes it possible to prepare an infinite number of
new MOFs with myriad structures and great potential for diverse applications [86,87]. The
efficiency of different MOFs: HKUST-1, MOF-5 and MIL-53(Al) has been assessed to extract
parabens from cosmetics [53]. After a deep optimization of the experimental conditions,
HKUST-1 proved to be the most suitable sorbent. The whole d-SPE(MOF)-HPLC–DAD
showed very low LODs (<0.1 µg L−1 ), and only 0.05 g of cosmetic sample were required.
A SBA-15/polyaniline para-toluenesulfonic acid nanocomposite supporting d-SPE was
developed for the extraction of parabens from cosmetic products. The experimental param-
eters were optimized by a central composite design. Under the optimal conditions which
involve the use of only 10 mg of sorbent, the d-SPE (SBA-15/PANI-p-TSA-NCs)-HPLC-UV
method was satisfactory validated, showing LODs lower than 0.4 ng mL−1 [54].

2.5. Pressurized Liquid Extraction (PLE)

PLE is an advanced extraction technique that operates at high temperature and pres-
sure. The elevated temperature enhances the solubility of the analytes, breaking the
matrix–analyte interactions, and thus increasing the mass transfer. A clean-up step is
Molecules 2021, 26, 4900 14 of 31

frequently performed at the same time as extraction (in-cell clean-up) by adding sorbents at
the bottom of the extraction cell [16]. Although it requires solvent volumes similar to those
of UAE, PLE provides shorter extraction times, and the currently commercially available
instruments present a high degree of automatization.
PLE has been applied to determine UV filters, fragrances, preservatives, perfluorooc-
tanoic acid (PFOA) and its derivates [55–59], and for the simultaneous extraction of musks,
preservatives and plasticizers [60,61] in a broad range of cosmetics and personal care
products, including those intended for babies and children. The main advantage of PLE
is that it drastically reduces the extraction time compared to traditional techniques. For
example, only 5 min are needed to extract preservatives, obtaining recoveries ranging from
75 to 119% [60]—whereas UAE or SLE require between 10 and 30 min [28,32]. In addition,
depending on the instrumentally available extraction cells, it can be easily miniaturized,
reducing the sample size by up to five times and the extraction volume up to two times [55].
Analytical determination after PLE has usually been performed by LC–MS/MS for the
most polar compounds such as UV filters or PFOA derivatives [55,59], whereas a derivati-
zation step, mainly acetylation with acetic anhydride and pyridine, was simultaneously
performed with the extraction before GC-MS analysis for the most polar target analytes’
determination such as UV filters and preservatives [56,61].

2.6. Matrix Solid-Phase Dispersion (MSPD)

In comparison with other extraction techniques that use high pressure such as PLE,
or the application of supplementary energy such as UAE, MSPD extraction is performed
under ambient conditions, without requiring any special equipment. In addition, the
possibility of performing extraction and an in situ clean up would reduce the sample
preparation time and decrease the required amount of solvent [88]. MSPD was introduced
in 1989 by Barker et al. for the determination of drug residues in animal tissue [89]. Since
then, it has attracted growing interest for its versatility and possibility of application to
a broad range of solid, semisolid, or viscous matrices. The general procedure consists
of the direct mechanical blending of the sample (with a dispersant agent) in a mortar
until an homogeneous and dispersed material is obtained, that is then transferred to a
cartridge and compressed. Analytes’ elution is performed by passing through the column
the correspondent solvent by gravity or vacuum assisted.
MSPD’s first application to cosmetics samples was in 2011 to determine fragrance
allergens and multiclass preservatives (parabens, bromine derivatives and antioxidants)
in rinse-off and leave-on cosmetics [62,63] as well as in baby care products [61] before
GC–MS analysis. The most critical experimental parameters such as dispersant, elution
solvent and volume were optimized by DoE (design of experiments) to obtain the highest
extraction efficiency. In all cases, the experimental conditions involved the use of 0.5 g of
the sample, 2 g of Florisil® as dispersant agent, and elution was accomplished with 5 mL of
hexane/acetone (1:1, v/v). For preservatives’ determination, the MSPD-obtained extracts
were derivatized by employing anhydride acetic to improve the chromatographic analysis
of those containing hydroxyl groups such as parabens. The acetylation procedure was also
optimized to obtain a quantitative reaction yield in a short amount of time (10 min) [63].
Another family of preservatives, isothiazolinones, were also successfully extracted from
cosmetic matrices by MSPD. In this case, methanol resulted as the optimal elution solvent,
and LC-MS/MS analysis was performed [64]. In all cases, quantitative recoveries and
LODs at the low ng g−1 were obtained, which were well below the legal requirements for
those restricted compounds [2].
In order to reduce the sample and solvent consumption, a miniaturization of the classi-
cal MSPD, µ-MSPD, was proposed by Llompart et al. for the first time in 2013 for the simul-
taneous analysis of plasticizers (phthalates and adipates) and synthetic musks in cosmetics
and personal care products [65]. Figure 2 schematically represents the µ-MSPD procedure.
 μ
Molecules 2021, 26, 4900 15 of 31
μ

Figure 2. μ
General µ-MSPD procedure employing a glass Pasteur pipette substituting
classical cartridges.

μµ-MSPD was subsequently successfully applied for the determination of other cos-
metic ingredients including dyes, fragrances, preservatives [66–71], as well as for the
multianalyte determination of a high number of allowed and restricted ingredients, in
addition to banned compounds such as glucocorticoids [72,73,75]. Recently, this minia-
turized approach was also applied to extract impurities or unexpected compounds such
as polycyclic aromatic hydrocarbons (PAHs), fungicides, nitrosamines, or alkylphenol
ethoxylates (APEOs) from cosmetics formulations. In this case, analysis was performed
by GC-MS or LC-MS/MS, depending on the chemical properties of the target analytes. In
general, obtained LODs were at the very− low ng g−1 concentration levels, showing that
the combination
μ of µ-MSPD with chromatography and mass spectrometry detection is a
suitable option to determine the trace levels of impurities and banned compounds with a
different chemical nature [74].
It is important to highlight that the use of theμµ-MSPD approach allows a reduction
in the extraction costs, since it employs disposable common laboratory use material such
as pipette tips or glass Pasteur pipettes [65,69,70,72–74]. The substitution of the classical
plastic MSPD cartridges for glass material is a very suitable and low-cost option for
the determination of ubiquitous compounds such as plasticizers, also reducing possible
interference during sample preparation [65,73,74]. Other advantages μ of the µ-MSPD in
comparison with classical MSPD is the reduction in the sample amount, reagents, and
organic solvents consumption. In most cases, satisfactory results were achieved employing
only between 0.05 and 0.1 g of sample [65,67–74] and Florisil® [65,67,70,72–74] as the
dispersant agent, although the use of other dispersants such as C18 [66] or sand [68] has
been reported. Recently, the use of monodisperse molecularly imprinted microspheres
(MMIMs) has been successfully proposed to extract glucocorticoids, banned compounds,
from cosmetics [75]. The combination of MMIM-MSPD achieved satisfactory recoveries
(approximately 90%) and precision (RSD values lower than 6%).
Regarding the elution solvent, ethyl acetate showed the highest extraction efficiency
for most of the target compounds before GC analysis [65,69,70,73,74], whereas MeOH
was the preferred elution solvent for µ-MSPD extractions before LC analysis [66–68]. The
μ
use of green solvents such as supramolecular solvents (SUPRASs) has also recently been
reported to extract parabens from cosmetics [71], constituting an environmentally friendly
alternative to classical organic solvents.
Molecules 2021, 26, 4900 16 of 31

2.7. Microextraction Techniques for Cosmetic Analysis

Microextraction techniques involve the use of a small volume of the extraction phase
in relation to the sample volume. Although microextraction techniques could not be
exhaustive procedures compared with classical ones, they have the advantage of being
almost solvent-free and therefore, more sustainable and easily implemented—key factors in
current developments for cosmetics analysis [15,90]. The most relevant sample preparation
developments for cosmetics analysis based on liquid-phase (liquid-liquid microextraction
(LLME), dispersive liquid–liquid microextraction (DLLME), ultrasound-assisted emul-
sification microextraction (USAEME)) and sorbent-phase (solid-phase microextraction
(SPME), fabric-phase sorptive extraction (FPSE), stir bar sorptive dispersive microextrac-
tion (SBSDME)) microextraction techniques are shown in Table 2.

2.7.1. Liquid-Phase Microextraction Techniques

Compared with conventional LLE, liquid-phase microextraction (LPME) is faster and
more environmentally friendly since a minimal amount—a few microliters—of organic sol-
vents is required. Due to the high ratio of sample volume: extracting solvent, high analytes
enrichment can be obtained. In recent years, liquid-based microextraction techniques have
become one of the preferred techniques for the extraction of different analytes from various
foods and environmental matrices [91]. However, their application for cosmetics analysis
may be a challenge due to the high matrix complexity of these products. In this sense,
preliminary sample pre-treatments such as sample dilution in organic solvents or water,
vortex agitation or UAE are usually required to obtain a liquid phase before LPME. Further
steps after extraction are also implemented to concentrate the analytes before analysis [92].
The most employed liquid-based microextraction techniques for cosmetics analysis have
been liquid–liquid microextraction (LLME), dispersive-LLME (DLLME) and ultrasound-
assisted emulsification microextraction (USAEME). The most relevant methodologies are
included in Table 2 and are commented on below.
Molecules 2021, 26, 4900 17 of 31

Table 2. Microextraction techniques for cosmetics analysis. Liquid-phase (LLME, DLLME, USAEME) and sorbent-based (SPME, FPSE, SBSDME) methodologies.

Extraction/
Sample Sample Extraction Extraction Post-Extraction Recovery RSD
Analytes Matrix Desorption Analysis LOD (ng mL−1 ) Ref.
Amount Pre-Treatment Technique Time (min) Treatment (%) (%)
Solvent
Liquid-Phase Microextraction Techniques for Cosmetics Analysis
Liquid–liquid Microextraction (LLME)
Evaporation,
4 alternative Dilution in 5 mL H2 O,
Creams, gels 0.1 g VA-LLME 1 mL hexane 0.3 reconstitution: HPLC-UV 84–118 20–60 <10 [93]
preservatives centrifugation
400 µL ACN
200 µL
Cosmetic- oil
4 preservatives 0.5 g VA-LLME (DES) [ChCl-Ethylene HPLC-UV >84 50–60 <3 [94]
products
glycol (1/2)]
Creams,
Bronopol 0.1 g VAEsME 0.5 mL H2 O 0.3 HPLC-UV 91–104 900 [95]
shampoos, gels
Dispersive Liquid–Liquid Microextraction (DLLME)
Aqueous
6 preservatives 5g Dilution in 100 mL H2 O DLLME 30 µL chloroform 2 GC-FID 81–103 5–25 <8 [96]
cosmetics
Dilution in 25 mL H2 O
Evaporation,
(lotion),
0.5 mL isopropyl reconstitution:
7 preservatives Lotions, creams 1g 5 mL EtOH (cream), DLLME HPCE 71–113 200–375 ng g−1 <5 [97]
alcohol MeOH/H2 O
vortex. UAE,
(20:80, v/v)
centrifugation
Dilution in 10 mL H2 O,
vortex + 0.2 g NaCl + 3.5
mL hexane, vortex, Evaporation,
centrifugation + 250 µL reconstitution: 30 µL
Acrylamide Creams, gels 0.15–0.5 g DLLME 80 µL chloroform 5 LC-UV 85–112 0.7–2.4 ng g−1 <14 [98]
ethanolic EtOH/H2 O
2-naphthalenethiol (aq) (50:50, v/v)
+ 250 µL di-sodium
tetraborate (aq), MW
Dilution in 1.5 mL H2 O
Atranol, + 1.5 mL hexane, vortex,
Perfumes 1 mL DLLME 100 µL chloroform 5 GC-MS 79–110 3–5 <9 [99]
chloroatranol centrifugation + 8 mL
H2 O + 1 mL K2 CO3 (aq)
Moisturizer,
Sample dilution (1:100),
1 preservative toner, lotion, VA-DLLME 5 mL chloroform 5 UV-Vis 82–97 476 <6 [100]
filtration
soap
Dilution in 200 µL
MeOH, vortex, UAE.
4 preservatives Cream, lotion 0.05 g VA-DLLME 100 µL DES 4 HPLC-DAD 0.3–2 [101]
Dilution in H2 O (1:100),
centrifugation
Shampoos, gels,
Dilution in 3 mL ACN, Evaporation,
creams, HPLC-DAD, 0.04–0.45
6 phthalates 0.03 g UAE, centrifugation, US-DLLME 150 µL CCl4 2 reconstitution: 25 µL 84–124 <10 [102]
deodorants, LC-MS/MS (LC-MS/MS)
filtration ACN
makeup
Molecules 2021, 26, 4900 18 of 31

Table 2. Cont.

Sample Sample Extraction Extraction/Desorption Extraction Post-Extraction Recovery RSD

Analytes Matrix Analysis LOD (ng mL−1 ) Ref.
Amount Pre-Treatment Technique Solvent Time (min) Treatment (%) (%)
Evaporation,
5 UV filters Sunscreens 0.4 mL US-VA-DLLME 160 µL anisole 5 reconstitution: 20 µL HPLC-DAD 88–105 15 <3 [103]
2-VNT
Face masks,
UNE-DLLME
6 parabens cream, hair 0.05 g 200 µL octanol 10 GC-FID 82–109 2000–9500 ng g−1 <5 [104]
(35 W)
conditioner
Magnetic stirring
2 dyes Lipsticks 50 mL 500 µL acetone 6 HPLC-DAD 90-95 1 <3 [105]
assisted-DLLME
Creams, Evaporation,
PLE, dilution to 50 mL
Vitamin E make-up, 0.5 g DLLME 100 µL CCl4 3 reconstitution: 15 µL HPLC-DAD 87–115 3–15 ng g−1 <8 [106]
ACN, filtration
shampoos MeOH
Evaporation,
Eau de toilette, Sample dilution and 150 mL of
1 dye IL-DLLME reconstitution: 260 mL HPLC-UV 99–103 0.34 ng <1 [107]
shampoos pH =4 adjustment [C10MIM][BF4]
MeOH
MSPE, UAE,
centrifugation + 100 µL 100 µL
1 preservative 1g IL-DLLME 10 HPLC-DAD 75–98 140 <7 [108]
Fe3 O4 NPs suspension + [C6 MIM][PF6 ]
20 mL H2 O, vortex
Toner, lotion,
Dilution in 3 mL ACN,
4 phenolic make-up IL-DLLME +80 µL [C8MIM]
1 mL UAE, dilution in 5 CE 82–119 5–100 <13 [109]
compounds remover, [PF6]
10 mL H2 O
perfume
Centrifugation, pH = 4 40 mg Supernatant + 500 µL
6 oestrogens Lotion IL-DLLME 5 LC-UV 96–111 5–15 <10 [110]
adjustment, filtration [P6,6,6,14 + ]2 [CoCl4 2− ] ACN
Sample dilution in 100
30 µL C8 Gu-Cl + Microdroplet dilution
4 parabens Facial tonics mL NaCl (aq, 8% w/v, IL-DLLME 5 HPLC-DAD 82–114 0.5–1.4 <16 [111]
45 µL Li-NTf2 to 60 µL ACN
pH = 5)
10 phthalates Emulsions 0.3 g DLLME-SFO 20 µL 1-dodecanol 10 Ice bath (5 min) LC-UV <4 [112]
Lipsticks, eye 1 mL EtOH/H2 O Placing into an
14 colorants 0.1 g Homogenization MA-DLLME-SFO 8 HPLC-DAD 90–106 250–3200 ng g−1 <3 [113]
shadows (pH = 4, 95:5, v/v) ice-bath, filtration
Creams,
IC-non-
3 sunscreen,
UA-LDS-DLLME suppressed
alkanolamines, lotions, 0.25 g 1 mL cyclohexane 15 Filtration 87–109 72–120 <6 [114]
(2.5 mM MSA) conductivity
2 alkylamines shampoos,
detection
powders
Mixture with 0.2
7 N- Creams, shower
0.1 g Na2 SO4 + 5 mL of RP-DLLME 75 µL H2 O 0.5 LC–MS 80–113 2–50 ng g−1 <10 [115]
nitrosamines gels
hexane, centrifugation
Creams, shower Dilution in 5 mL
NDELA 0.1 g RP-DLLME 125 µL H2 O 5 HPLC-UV 87–117 1.1 <8 [116]
gels toluene, centrifugation
Molecules 2021, 26, 4900 19 of 31

Table 2. Cont.

Sample Sample Extraction Extraction/Desorption Extraction Post-Extraction Recovery RSD

Analytes Matrix Analysis LOD (ng mL−1 ) Ref.
Amount Pre-Treatment Technique Solvent Time (min) Treatment (%) (%)
Gels, masks, Mixture with 0.4 g
Free
creams, 0.01–0.1 g MgSO4 + 5 mL toluene, RP-DLLME 50 µL H2 O 5 HPLC-UV 91–113 0.7–2.3 <9 [117]
formaldehyde
shampoos centrifugation
Ultrasound-Assisted Emulsification Microextraction (USAEME)
Dilution in 20 mL
Sunscreen, MeOH, UAE,
5 preservatives shampoos, 0.1–0.25 g centrifugation. Dilution USAEME 40 µL 1-octanol HPLC-UV 22–102 0.3–8.3 <10 [118]
toothpastes to 50 mL MeOH.
Dilution
Dilution of the IL
125 µL extraction solution
9 hormones Cosmetics 0.2 g IL-USAEME 27 LC 86–109 100–900 ng g−1 <3 [119]
[C7MIM][PF6] (~100 µL) to
1 mL MeOH
Eau de toilettes,
18 fragrance Dilution with
colognes, USAEME-SFOD 50 µL 2-dodecanol 10 HPLC-DAD 90–138 1–154 <12 [120]
allergens 20 µL MeOH
perfumes
Dilution in 100 µL
Shampoos, after
MeOH + 10 mL H2 O.
5 phthalates shave gels, hair 0.03 g USAEME-SFO 30 µL 1-undecanol 12 HPLC-DAD 0.005–0.01 [121]
Hair spray: Dilution in
sprays
MeOH
0.02 g
Skin cleansers, Dilution in 10 mL H2 O
(skin 125 µL 1-octanol +
toothpastes, or MeOH, UAE,
5 preservatives cleanser), UASEME 50 µL tween 20 6 HPLC-UV 70–138 0.03–10 <7 [122]
creams, filtration. Dilution to
0.05 g solution
sunscreens 500 mL
(other)
Sorbent-Based Microextraction Techniques for Cosmetics Analysis
Solid-Phase Microextraction (SPME)
Balms, creams, SPME (PDMS/DVB
24 fragrance
deodorants, 1 mL fibre, HS, 20 GC-FID 80 7–2700 <6 [123]
allergens
toothpastes 40 ◦ C, 20 min)
Rinse-off, Dilution in 10 mL H2 O + SPME
16
leave-on 0.1 g 20% NaCl, w/v + (PDMS/DVB/CAR 15 GC-MS/MS >85 6–780 ng g−1 <13 [124]
preservatives
cosmetics derivatization fibre, DI, 40 ◦ C)
Rinse-off Dilution in 10 mL H2 O + SPME (PDMS/DVB
Bronidox 1 mL 30 GC-µECD 70–92 60 ng g−1 <10 [125]
cosmetics 20% NaCl (aq) fibre, DI)
11 Creams, hair SPME (PDMS/DVB
0.1 g UV radiation 20 Dilution GC-MS 54–111 31–170 ng g−1 <12 [126]
preservatives conditioners fibre, DI)
SFE-online-SPME
(SFE-CO2 (55 ◦ C,),
Emulsions,
6 preservatives 0.02 g derivatization + 25 GC-MS 89–172 0.5–8.3 ng g−1 <8 [127]
lotions, creams
SPME (PA fibre, HS,
50 ◦ C)
Molecules 2021, 26, 4900 20 of 31

Table 2. Cont.

Sample Sample Extraction Extraction/Desorption Extraction Post-Extraction Recovery RSD

Analytes Matrix Analysis LOD (ng mL−1 ) Ref.
Amount Pre-Treatment Technique Solvent Time (min) Treatment (%) (%)
Purge-and-trap-
Dilution in 4 mL H2 O, Portable
BHT 0.1 g NTD (PDMS/DVB 30 90–99 <10 [128]
vortex, centrifugation GC-MS
fibre, HS, 60 ◦ C)
SPME (Aluminium
Shampoos, body
NDELA 10 mL Dilution in H2 O hydroxide grafted 15 GC-MS 95–99 1 ng g−1 <6 [129]
gels, hands soaps
fibre, HS, 70 ◦ C)
Sunscreen, Sample dilution (1:25, SPME (PEG-DA Desorption: 1 mL
4 preservatives 20 HPLC-DAD 90–98 120–150 <7 [130]
lotions, creams w/v) in NaCl (aq), UAE fibre, DI, 65 ◦ C) MeOH, filtration
SPME (C3 N4 @G
6 PAHs Cosmetics 0.3 g Dilution in 50 mL H2 O 35 GC-MS 70–118 0.001–0.002 <12 [131]
fibre, DI, 40 ◦ C)
6 fragrance Shampoos, SPME (β-CD/GO
0.05–0.1 g Dilution in 100 mL H2 O 40 GC-FID 70–94 0.05–0.15 <11 [132]
allergens creams fibre, HS, 70 ◦ C)
SPME
Mixture with API® 10S +
MVOCs Hands cream 0.1 g (PDMS/DVB/CAR 30 GC-MS [133]
incubation (37 ◦ C, 24 h)
fibre, HS, 60 ◦ C)
Shampoos, SPME
Dilution in 2 mL H2 O +
MVOCs creams, gels, 0.1 g (PDMS/DVB/CAR 30 GC-MS [134]
bacterial culture
make-up fibre, HS, 60 ◦ C)
Fabric phase sorptive extraction (FPSE)
FPSE
3 preservatives MeOH Filtration HPLC-DAD 2.7–3.0 <4 [135]
(CW-20 coating)
Rose waters, Sample dilution in H2 O,
0.1 g
5 preservatives deodorants, filtration, UAE, FPSE (PEG coating) 0.5 mL MeOH 25 Filtration HPLC-DAD 88–122 0.2–0.6 <5 [136]
(cream)
serums, creams centrifugation
Stir bar sorptive dispersive microextraction (SBSDME)
SBSDME
Dilution in 25 mL NaCl Filtration, evaporation,
8 N- Shower gels, (CoFe2 O4 /MIL-
0.5 g (aq), vortex + 1 mL 1 mL acetone 30 reconstitution: 50 µL LC-MS/MS 96–109 3–13 ng g−1 <17 [137]
nitrosamines body creams 101(Fe)
hexane. Centrifugation H2 O
stir bar)
Dilution in 40 mL SBSDME
Creams, milks,
10 PAHs 4g hexane, vortex, (CoFe2 O4 -rGO 0.5 mL toluene 10 Filtration GC-MS 0.1–24 ng g−1 <10 [138]
body-milks
centrifugation stir bar)

2-VNT: 2-vinylnapthalene; API: analytical profile index; CAR: carboxen; CE: capillary electrophoresis; CMA; chlormadinone acetate; DAD: diode array detector; DES: deep eutectic solvent; DI: direct immersion;
DVB: divinylbenzene; ECD: electron capture detector; EtAc: ethyl acetate; EtOH: ethanol; FID: flame ionization detector; GC: gas chromatography; HPCE: high-performance capillary electrophoresis; HPLC:
high-performance liquid chromatography; HS: headspace; IC: ion chromatography; IL: ionic liquid; LDS: low-density solvent; LOD: limit of detection; LOQ: limit of quantification; MA: microwave-assisted;
MeOH: methanol; MS: mass spectrometry; MSPE: magnetic solid-phase extraction; NDELA: N-nitrosodiethanolamine; NPs: nanoparticles; NTD: needle trap device; PA: polyacrylate; PEG: polyethylene glycol;
PDMS: polydimethylsiloxane; PLE: pressurized liquid extraction; RP: reversed phase; RSD: relative standard deviation; SFO: solidification of the floating organic; THF: tetrahydrofuran; UAE: ultrasound-assisted
extraction; UASEME: ultrasound-assisted surfactant-enhanced emulsification microextraction; UNE: ultrasonic nebulization; US: ultrasonic radiation; UV: ultraviolet; VA: vortex-assisted; VAEsME: vortex-assisted
emulsification semi-microextraction.
Molecules 2021, 26, 4900 21 of 31

Liquid–Liquid Microextraction (LLME)

LLME was successfully employed to extract alternative preservatives from creams and
gels [93]. Extraction was vortex-assisted (VA) to improve its efficiency and a chromophoric
in situ derivatization step employing benzoyl chloride was implemented to enhance
the analytical response of the target compounds [93]. The combination of deep eutectic
solvent (DES) with LLME is one of the novel trends in LPME. DES are considered new
and green solvents that can be used in the development of new liquid-based methods.
DES-VA-LLME was recently proposed to determine parabens in cosmetics oil products.
The employed DES was prepared with choline chloride and ethylenglycol [94]. The
whole DES-DLLME-HPLC-UV method showed good recoveries and LODs at the low
parts per billion [94]. A variation of VA-LLME, called vortex-assisted emulsification
semi-microextraction (VAEsME) was successfully proposed for the determination of the
preservative bronopol in cosmetics followed by HPLC-UV [95]. This approach allowed a
fast one-step solution-extraction procedure which is very useful for the determination of
ingredients with restricted concentrations, such as bronopol.

Dispersive Liquid–Liquid Microextraction (DLLME)

DLLME was introduced by Rezaee et al. in 2006 [139]. In DLLME, a small volume
of extracting solvent is dispersed by the action of a second solvent into the sample. The
abundant contact surface of the fine droplets and the solvent phase greatly enhances the
extraction efficiency, thus reducing the solvent volume needed and the extraction time [140].
DLLME has been applied for the cosmetics’ extraction of a broad range of compounds
including preservatives, fragrances, phthalates, and acrylamide [96–102]. The most critical
experimental parameters affecting DLLME such as dispersive solvent, extraction solvent
and volume, and extraction time, were optimized to obtain the highest extraction efficiency.
High density solvents such as chloroform [96,98–100], dichloromethane [97] or carbon
tetrachloride [102] were the most employed ones, although the use of environmentally
friendly alternatives, such as polymeric DES composed of DL-menthol and polyethylene
glycol, has been proposed for the extraction of parabens from leave-on cosmetics [101].
Recently, anisole, a bio-derived solvent, was employed for the DLLME of UV filters from
sunscreens, showing its suitability as a green alternative to classical organic solvents, not
only to determine the target compounds’ concentration in the formulations, but also in
the skin after sunscreen application [103]. To improve the dispersion of the solvent into
the cosmetic matrix, VA-DLLME has been mainly employed [100,101], although the use of
ultrasonic radiation (US), ultrasonic nebulization (UNE) or magnetic-stirring to assist in
the DLLME of parabens, phthalates, UV filters and dyes have been also reported [102–105].
For some analytes, especially for the more polar ones such as atranol and chloroatranol, in
situ derivatization was performed to enhance their chromatographic response before GC
analysis [99]. The use of DLLME-HPLC-DAD after performing other advanced extraction
techniques such as PLE has also been proposed as an effective tool to determine vitamin E
in cosmetics [106], showing good recoveries and LODs at the low ng g−1 .
Other novel approaches in DLLME include methodologies based on ionic liquids
(ILs), the solidification of the floating organic droplets (SFOD) or the use of low-density
solvents (LDS) to substitute the use of organic solvents. IL-DLLME has been proposed as
an environmentally friendly alternative prior to HPLC-DAD or CE analysis to extract dyes,
preservatives, phenolic compounds or estrogens from cosmetics [107–111]. Methodolo-
gies based on DLLME-SFO were successfully employed for the extraction of phthalates
from aqueous cosmetics [112] as well as for dyes from lipsticks [113]. In the last case,
the extraction and clean-up steps were integrated to simplify the operation, achieving a
high-throughput sample preparation. The main factors affecting the extraction efficiency
were optimized by multi-response surface methodology and the validated method was
applied to more than 120 cosmetics samples. The performance of DLLME-SFO was com-
pared with LLE, UAE and classical DLLME, showing that DLLME-SFO was the most
effective technique to extract phthalates from complex cosmetics matrices [109]. The use of
Molecules 2021, 26, 4900 22 of 31

cyclohexane, a low-density and less toxic solvent to disperse the sample (LDS-DLLME) was
proposed for the determination of alkanolamines and alkylamines [114]. This approach
allows the target analytes to transfer into acidic solutions, while liposoluble substances
were dissolved in cyclohexane. The complete extraction was accomplished within 13 min
and further purification, or clean-up steps were not necessary.
One decade ago, Hashemi et al. [141] proposed a modification of the original DLLME
called reversed-phase DLLME (RP-DLLME), where a small volume of water, used as
extraction solvent, is dispersed into a bulk organic solution containing the polar target
analytes. RP-DLLME has recently been applied to extract n-nitrosamines [115,116] and
free formaldehyde [117] from cosmetics and personal care products before LC-MS [115] or
HPLC-UV analysis [116,117]. In all cases, the employed volume of water ranged between
50 and 125 µL, with recoveries and LODs similar to those obtained for the analysis of free
formaldehyde by UAE-CPE-UV-Vis [40] or n-nitrosamines employing SPE-LC-MS/MS [44].

Ultrasound-Assisted Emulsification Microextraction (USAEME)

USAEME was introduced by Regueiro et al. in 2009 [142]. It relies on the emulsification
of the organic extractant in the sample by ultrasonic energy without the need for a disperser
solvent, which favours efficiency, achieving the complete extraction of the analytes into
the organic phase. This technique shows the advantage of using US to accelerate the mass-
transfer process between two immiscible phases, reducing the extraction time. USAEME
has been applied to extract preservatives, hormones, fragrances and phthalates from
cosmetics matrices [118–122].
The use of ionic liquids (ILs) to substitute the organic solvents (IL-USAEME) has been
proposed as an environmentally friendly alternative prior to HPLC-UV to determine three
glucocorticoids, one androgen and five progestogens in cosmetics [119]. The combination
of USAEME with SFO was applied to determine fragrances and phthalates in both rinse-off
and leave-on cosmetic samples [120,121]. In both cases, a few microliters of 2-dodecanol
and 1-undecanol were employed, respectively, to perform the extraction. Several parame-
ters influencing the extraction efficiency were optimized. Another environmentally friendly
approach involves the use of ultrasound-assisted surfactant-enhanced emulsification mi-
croextraction (UASEME), that employs a surfactant and less toxic organic solvent which
offers an environmentally friendly procedure. A method based on UASEME-HPLC-UV
to determine preservatives in different cosmetic samples was developed. Obtained LODs
were similar to those provided by classical USAEME [118].

2.7.2. Sorbent-Based Microextraction Techniques

Although LPME approaches are simple and do not require expensive apparatus, they
usually require several steps, and their automation is more complex than that required by
sorbent-based microextraction techniques. In addition, the sorbent material can usually
be reused, and the procedure implies minimum solvent consumption or even completely
eliminating the organic solvents in the whole experimental procedure. Besides, a wider
variety of sorbent-based microextraction techniques have been developed in recent years in
comparison to LPME, likely due to the versatility of different sorbent materials that can be
(i) packed in a small device; (ii) dispersed along the sample matrix, or (iii) coated on a solid
support [143]. The most employed sorbent-based microextraction technique for cosmetics
analysis has been solid-phase microextraction (SPME); however, in recent years, the appli-
cation to cosmetics of recently developed sorbent-based microextraction techniques such
as fabric phase sorptive extraction (FPSE) or stir bar sorptive dispersive microextraction
(SBSDME) is increasing with promising results. The most relevant methodologies are
included in Table 2 and are commented on below.

Solid-Phase Microextraction (SPME)

SPME was introduced in 1989 by Pawliszyn et al. [144]. Nowadays, it is a well-
established green solvent-free extraction technique with a large number of applications
Molecules 2021, 26, 4900 23 of 31

in different fields such as food, forensic, biomedical and the environment [145]. One
of the main advantages of SPME is that extraction and analytes’ pre-concentration are
performed in a single step. In addition, SPME allows the possibility to directly sample
the vapour phase in equilibrium with the matrix (headspace (HS) mode), or the matrix
extract or solution (direct immersion (DI) mode). Nowadays, a high number of commer-
cially available SPME fibres exist, such as polydimethylsiloxane (PDMS), polyacrylate (PA),
polydimethylsiloxane/divinylbenzene (PDMS/DVB), carboxen (CAR) or polydimethyl-
siloxane/divinylbenzene/carboxen (PDMS/DVB/CAR), among others. The fibre coating
selection depends on the target analytes’ properties. Two of the most employed ones for
cosmetics analysis were PDMS/DVB and PDMS/DVB/CAR, used to extract fragrance
allergens or preservatives [123–125], showing good performance in terms of accuracy,
precision and low LODs. However, in recent years, trends in SPME for cosmetics are
moving towards the development of novel sorbent coatings since commercially avail-
able fibre coatings are limited and restrict the wide application of this microextraction
technique, especially for multitarget analysis. In this sense, the aluminium hydroxide
grafted fused silica SPME fibre was successfully prepared by means of a grafting process
for the first time to determine the n-nitrosamine NDELA in cosmetics. The homemade
fibre showed good thermal stability, up to 500 ◦ C, as well as a satisfactory repeatability
with RSD values lower than 6% [129]. A poly(ethylene glycol) diacrylate (PEG-DA) fibre
was proposed to determine parabens in cosmetics products [130]. The PEG-DA polymer
coating was covalently attached to the fibre by introducing a surface modification with
3-(trichlorosilyl)propyl methacrylate (TPM). This approach leads to an increase in the
surface area, improving the extraction efficiency and showing good repeatability (fibre-
to-fibre), although obtained LODs were higher than those provided by commercial fi-
bres [124,127]. The use of single-layer graphitic carbon nitride-modified graphene compos-
ite (C3 N4 @G), as well as β-cyclodextrin/graphene oxide-modified fibres were employed
for the extraction of PAHs and fragrances, respectively [131,132]. In most cases, GC analysis
was carried out after SPME [123–125,127–129,131,132], directly performing analytes’ des-
orption in the instrument injector—although LC analysis has also been employed [130]. In
this last case, the desorption was performed, employing a small volume of organic solvent.
The combination of different extraction techniques with SPME is attracting signif-
icant attention. For example, µ-MSPD in combination with SPME was employed as a
fast and reliable tool to extract multiclass preservatives (benzoates, parabens, triclosan,
butylhydroxy-toluene and butylhydroxyanisole) from cosmetics as well as to monitor their
photo-transformation after solar radiation [126]. This is important since cosmetics, espe-
cially leave-on ones, are in prolonged contact with the skin, and exposure to solar radiation
may not only cause the inactivation of the preservatives, but may also produce potentially
hazardous photoproducts. The combination of supercritical fluid extraction (SFE)-online-
SPME has been employed to extract multiclass preservatives including parabens and
antioxidants from cosmetics [127]. The analytes were extracted from the matrix with su-
percritical CO2 . Since analysis was performed by GC-MS, an in situ derivatization step
was necessary to improve the chromatographic peak shape of the parabens. Finally, ana-
lytes were adsorbed on a polyacrylate (PA) fibre. The combination of a purge-trap with a
headspace needle trap device (NTD) and portable GC-MS analysis has also recently been
proposed to determine the antioxidant BHT in cosmetics [128], demonstrating the feasi-
bility of utilizing a hand-portable GC-MS for the real-time estimation of this compound,
facilitating quality control measurements by inspecting agencies.
SPME has also been proposed as a very promising, non-invasive, and fast technique to
evaluate the presence of bacteria (Escherichia coli, Pseudomonas aeruginosa, or Proteus mirabilis
among others) in cosmetics. Most of the currently employed techniques for this purpose,
including the official methodology, are based on the colony-forming units (CFUs) count
and although they employ low-cost materials, they are laborious and require several steps,
also being highly time consuming (up to 72 h). It is well known that bacteria produce mi-
crobial volatile organic compounds (MVOCs), which are formed during bacterial metabolic
Molecules 2021, 26, 4900 24 of 31

processes. This way, SPME employing commercial PDMS/DVB/CAR fibres has been
employed to perform an in situ extraction and preconcentration of the MVOCs in a sin-
gle step [133,134]. Afterwards, GC-MS has been employed as determination technique
to unequivocally identify the MVOCs derived from the enzymatic activity, allowing the
identification of several of them as specific markers for each one of the studied bacteria, as
well as others as general indicators of bacteria presence.

Fabric-Phase Sorptive Extraction (FPSE)

Fabric phase sorptive extraction (FPSE) has recently been developed by Furton’s and
Kabir’s group [146]. FPSE uses small squares of cellulosic (or other) fabric coated with
a thin sol–gel, which are directly immersed in the samples to sorb and extract analytes.
Analytes’ desorption is performed by immersing the FPSE device into a small volume of
solvent and can be assisted by US or vortex agitation to accelerate the analytes’ transfer
to the solvent. The use of a fabric-phase sorptive extraction membrane provides a high
surface area which offers high sorbent loading, shortened equilibrium time, and an overall
decrease in the sample preparation time. It has mainly been applied to extract different
organic contaminants from environmental matrices [147].
Although it is a very recent extraction technique, it has been applied, followed by
HPLC-DAD, to the determination of parabens in cosmetics [135,136]. The main experi-
mental parameters affecting extraction such as FPSE membrane coating, sample pH, or
desorption solvent were optimized, showing that both carboxen (CW-20) and PEG mem-
brane coatings were suitable to extract parabens. Satisfactory recoveries and precision were
achieved and LODs at the ng mL−1 were obtained. The FPSE membrane can be reused
several times without losing extraction efficiency, showing the suitable applicability of this
recent technique to cosmetics.

Stir Bar Sorptive Dispersive Microextraction (SBSDME)

Among the sorbent-based microextraction techniques, stir bar sorptive dispersive
microextraction (SBSDME) is one of the most recent ones. It was introduced by Benedé
et al. as a hybrid microextraction technique that combines the principles of stir bar sorptive
extraction (SBSE) and dispersive µ-solid-phase extraction (dµSPE) [148]. It has been mainly
applied to determine organic contaminants in the aquatic media [149]. Although it is a
very recent technique, its use has been extended to cosmetics matrices using a hybrid
magnetic composite made of CoFe2 O4 MNPs and MIL-101(Fe) MOF as a sorbent phase to
analyse N-nitrosamines [137] and a magnetic carbonaceous composite made of CoFe2 O4
and reduced graphene oxide (rGO) to extract PAHs [138]. In both cases, satisfactory
recoveries and precision were achieved, showing the use of SBSDME as a promising green
microextraction technique.

3. Future Trends and Directions

In recent years, great efforts have been made to develop robust and reliable analytical
methodologies for cosmetics analysis. In this way, sample preparation plays an essential
role. Due to the high number of chemical compounds co-existing in these formulations,
the development of automated and fast procedures for the simultaneous extraction of a
high number of analytes in a single step is necessary. Extraction procedures such as SLE,
LLE, UAE, SPE, PLE or MSPD are still in use for cosmetics analysis. However, the trends
moving towards miniaturization allow reducing sample, solvent, and time consumption.
The improvements made in terms of the miniaturization and portability of extraction
devices greatly facilitate the implementation of these techniques in control laboratories
and in the performance of in situ analysis. Regarding microextraction techniques, to date,
SPME has been the most employed for its simplicity, non-organic solvent use and high
analytes’ enrichment. In addition, the variety of commercially available fibre coatings
is constantly growing, which are opening up the range for further applications in the
cosmetics analysis field. However, the application of recently developed techniques such as
Molecules 2021, 26, 4900 25 of 31

FPSE or SBSDME, that have mainly been applied to environmental analysis, in the field of
cosmetics is generating growing interest. The development of new sorbent materials such
as MWCNTs, LDHs or MIP-based coatings will continue being of particular interest to these
approaches. Further directions of research should also consist of developing analytical
tools to evaluate the presence of non-expected compounds, such as those of botanical
origin, since the presence of cosmetics containing ingredients of natural origin is growing,
assessing the stability of these compounds and evaluating the potential by-products formed
by photodegradation.

Author Contributions: Conceptualization, M.C.; writing—original draft preparation, M.C.; writing—

review and editing, M.C., C.G.-J., M.L. (Maria Llompart) and M.L. (Marta Lores); funding acquisition,
C.G.-J., M.L. (Maria Llompart) and M.L. (Marta Lores). All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by project ED431 2020/06 (Xunta de Galicia). The authors
belong to the National Network for the Innovation in miniaturized sample preparation techniques,
RED2018-102522-T (Ministry of Science, Innovation and Universities, Spain). This study was based
upon work from the Sample Preparation Study Group and Network, supported by the Division of
Analytical Chemistry of the European Chemical Society. All these programmes are co-funded by
FEDER (EU).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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