Results
All
menstrual products had detectable concentrations of plastic additives,
and a total of 5 PAEs, 16 OPEs, and 7 APs were detected ( Tables S8–S10 ). PAEs were detected in
all reusable sanitary pads and menstrual cups, but showed lower detection
frequencies in other products. OPEs were detected in 100% of all products,
except menstrual cups (detection frequency: 17%). Finally, for APs
the detection frequency was 100% across all products, reflecting a
more widespread use. Indeed, many APs are used as substitutes for
PAEs and OPEs that are regulated or considered of concern for environmental
and human health.
,
Plastic additives concentrations
varied depending on the product type ( Figure
). Differences were observed in terms of
both ng/g and ng/product concentrations (obtained by multiplying ng/g
concentrations by the product weights) ( Figure S2 ). For total plastic additives, significant differences were
observed among different products (Kruskal–Wallis rank sum
test: p -value < 0.05, Table S11 ). The highest total plastic additive concentrations were
found in reusable sanitary pads (median: 31856 ng/g; range: 6140 −47174
ng/g) followed by sanitary pads (median: 10014 ng/g; range: 4310–16197
ng/g) ≈ panty liners (median: 2075 ng/g; range: 271–13998
ng/g) ≈ menstrual underwear (median: 1960 ng/g; range: 424–4283
ng/g) ≈ menstrual cups (median: 1116 ng/g; range: 326–2454
ng/g) > tampons (median: 263 ng/g; range: 243–1027 ng/g).
( Figure
, Table S11 ).
∑ PAEs, ∑ OPEs, ∑APs,
and total plastic additives
concentrations (∑ PAEs + ∑ OPEs + ∑ APs) (ng/g)
in sanitary pads, panty liners, tampons, reusable sanitary pads, menstrual
underwear, and menstrual cups (note the different scales).
Considering the different classes of additives
analyzed,
reusable
sanitary pads had the highest concentrations of PAEs (median: 28856
ng/g; range: 5019–42193 ng/g) and OPEs (median: 1906 ng/g;
range: 158–4068 ng/g), but the highest concentrations of APs
were observed in the single-use sanitary pads (median: 8873 ng/g;
range: 2830–11455 ng/g). Tampons had the lowest concentrations
of PAEs (median: < LOD ng/g; range: < LOD-616 ng/g) and APs
(median: 145 ng/g; range: 113–525 ng/g), while the lowest OPEs
concentrations were found in menstrual cups (median: < LOD ng/g;
range: < LOD-98.0 ng/g) ( Figure
). The differences in concentrations between different
products were significant for all classes of additives (Kruskal–Wallis
rank sum test: p -value <0.05). However, even if
clear differences in median concentrations were observed among product
types, pairwise comparisons showed statistically significant differences
only between certain types ( Tables S12, S13, S14 ). The differences in concentrations might be attributed to product
design. Tampons consist of an absorbent material covered by a thin
synthetic fiber to facilitate application, while sanitary pads and
panty liners have multilayer compositions with one or more plastic
layers. Despite the similar design of sanitary pads and panty liners,
their composition can differ, since sanitary pads are designed for
regular/abundant menstrual flow, while panty liners are made to retain
small losses of blood/urine. Reusable sanitary pads and menstrual
underwear are different from single-use products since these are made
of textiles, often including synthetic fibers and a waterproof layer.
Lastly, menstrual cups differ from all other products and are made
solely of silicone or thermoplastic elastomer (TPE). Differences in
concentrations might also be due to the use of different polymers
and materials. However, since most products are composed of a combination
of multiple polymers that varies between different brands ( Table S2 ), it is not possible to conclude if
differences in plastic additive concentrations are driven by the materials
used.
APs were the main plastic additives in sanitary pads,
panty liners,
and menstrual underwear, but not in tampons, in which OPEs were the
dominant compounds, and reusable sanitary pads and menstrual cups,
in which PAEs were the dominant compounds ( Figure
). As mentioned earlier, APs are used as
replacements of PAEs and OPEs in many applications, including plastic
and textile materials,
,
and their more widespread detection
might reflect this shift. In most menstrual products, PAEs concentrations
were higher than OPEs, similar to other plastic-based products, such
as face masks,
,
textiles,
,
and food contact materials.
,
Only in tampons and
menstrual underwear were OPEs found in higher concentrations than
PAEs. Despite the regulation of some PAEs, these compounds are still
widely used in consumer products. It has been hypothesized that the
presence of PAEs in menstrual products, such as sanitary pads and
panty liners, might be coming from the plastic materials used on the
top/bottom layers. PAEs might also be used in sanitary pads and panty
liners in the adhesives added to these products or as fragrance fixatives,
since previous studies have observed higher PAEs concentrations in
sanitary pads with a scent applied compared to those without a scent.
,
The sample selection of the present study included both products
with and without a scent applied, but no clear differences in PAEs
concentrations and profiles were observed between scented and unscented
products ( Figure S3 ). However, since the
presence of scents was not a factor driving the sample selection,
this comparison might be limited by the low number of samples of sanitary
pads without a scent and panty liners with a scent applied. PAEs are
also widely used in the textile industry to produce synthetic fibers
and to give textiles waterproof properties. A waterproof layer is always included in reusable menstrual products,
and most of the products included in this study had at least one textile
layer made of a synthetic fiber, such as rayon, polyester, and elastane
( Table S2 ). Additionally, PAEs’
presence in menstrual underwear and reusable sanitary pads might be
due to the presence of these compounds in dyes, textiles inks, and
other processing aids and water used during textiles and product production. Previous studies also hypothesized that PAEs
in menstrual products might be coming from the product packaging.
In the present study PAEs, OPEs, and APs were detected in the packaging
of single-use products ( Table S15 ), and
a positive correlation between the concentrations in the product and
in the packaging was significant only for TBC and ATBC in panty liners
( Table S16 ). This suggests that the packaging
might indeed be a source of plastic additives in menstrual products
but that this might depend on the materials used in the product and/or
packaging since associations were only observed for panty liners.
Average
percentage contribution of PAEs, OPEs, and APs to total
plastic additives concentrations in sanitary pads, panty liners, tampons,
reusable sanitary pads, menstrual underwear, and menstrual cups.
Variability in composition between different products
was also
observed within the three classes of additives analyzed. Among the
5 PAEs detected in menstrual products, DEHP and DiNP were the major
components in reusable sanitary pads and menstrual underwear ( Figure
). DEHP concentrations
in reusable sanitary pads (median: 22825 ng/g; range: 4913–41929
ng/g) were at least 1 order of magnitude higher than in menstrual
underwear (median: 161 ng/g; < LOD-400 ng/g). DiNP was only detected
in one sample of reusable sanitary pads (14135 ng/g) and one sample
of menstrual underwear (2077 ng/g) from the same brand, but at high
concentrations. As for DEHP, DiNP concentrations in reusable sanitary
pads were higher than in menstrual underwear. This is consistent with
several studies reporting DEHP and DiNP among the main PAEs detected
in textile materials.
−
DEHP is the PAE consumed in greatest quantities by the textile industry,
and, similar to our findings, most of the literature on textile-based
products found DEHP to be the PAE present in the highest concentrations. An additional PAE, DiDP, was detected in all
reusable sanitary pads but at low concentrations (median: 91.1 ng/g;
54.7–192 ng/g) compared to DEHP and DINP. This PAE has also
been detected in other textile products.
, ,
DEHP (median: 116 ng/g; 36.1–1003
ng/g) and DiNP (median: < LOD ng/g; < LOD-1477 ng/g) were also
major components in menstrual cups, but with lower concentrations
than other reusable products. Additionally, in menstrual cups DBP
was found as a major additive, since it was detected in 5 out of 6
menstrual cups (median: 138 ng/g). DiDP was also detected in half
of the menstrual cups. Interestingly, DiNP was detected only in TPE
cups ( Figure S4 ). The presence of PAEs
in menstrual cups can be expected since these compounds are often
used to improve the flexibility of plastic materials. For single-use
products, DBP, DEHP, DiNP, and DiDP were also the compounds most frequently
detected, but the detection frequencies were lower, and their contribution
changed depending on the product type.
However, PAEs results
in sanitary pads, panty liners, and tampons
differed from those of previous studies
−
( Tables S17, S18 ). DBP was not detected in single-use sanitary
pads from our study but was detected in all sanitary pads analyzed
in previous studies. These studies reported the DBP isomers separately
with median concentrations between 73.0 and 1424 ng/g for DiBP and
between 83.3 and 909 ng/g for DnBP. Additionally, DEHP (detected only
in one sample from our study) and DMP (not analyzed in our study)
were also detected in most of the sanitary pads from previous studies.
PAEs in tampons and panty liners were only reported in one study by
Gao and Kannan. For DEHP, concentrations
from the Gao and Kannan study (mean: 744 ng/g for tampons, 2070 ng/g
for panty liners) were at least 1 order of magnitude higher than those
in our study (mean: 14.5 ng/g for tampons, 121 ng/g for panty liners).
In the Gao and Kannan study, DiBP and DnBP were quantified separately
and found to be in both product types. In our study, DiBP and DnBP
were not found in tampons but were quantified together in several
panty liners with concentrations lower than those reported in the
literature. These differences, observed between our study and previous
literature reports, might be due to changes in PAEs legislation and
production since the products in our study were collected during 2024,
while the products in previous studies were bought between 2016 and
2019.
−
The differences might also be due to differences
in PAEs legislation between the countries where the samples were purchased.
For example, the EU limits the application of BBzP, DBP, DEHP, and
DiDP in most consumer products, while the US regulates the same PAEs
only in child toys. Further, the analyzed
PAEs in the current study differ from those of previous studies, and
this discrepancy might also affect the differences observed in terms
of ∑ PAE concentrations.
OPEs also differed between
different menstrual products ( Figure
). TNBP was detected
only in single-use products and was the dominant OPE in sanitary pads
and panty liners with concentrations between 110 and 319 ng/g (median:
236 ng/g) and between < LOD-193 ng/g (median: 22.4 ng/g), respectively.
TNBP was also widely detected in tampons (detection frequency: 78%)
but at lower concentrations (median: 11.1 ng/g; range: < LOD-99.7
ng/g). A wide variety of other OPEs were detected in sanitary pads
and panty liners, but with detection frequencies <50% and concentrations
at least 1 order of magnitude lower than TNBP ( Table S9 ). TNBP is one of the OPEs most widely used as plasticizer
and this might explain its wide detection only in single-use products. In tampons, the dominant OPE was TCEP (median:
24.6 ng/g; range: 11.7–82.7 ng/g), which was detected in all
samples with concentrations comparable to those of TNBP. TCEP was
also detected in one sample of menstrual underwear at a high concentration
(216 ng/g). However, the main OPE in reusable sanitary pads and menstrual
underwear was TPHP, which was detected in 100% of both types of products
at high concentrations (median: 820 ng/g in reusable sanitary pads;
316 ng/g in menstrual underwear). TPHP is known to have applications
in textiles and textile coatings. In
menstrual cups, TEP was the only OPE detected, but only in one of
the samples analyzed.
Lastly, among the APs, ATBC was the dominant
compound in all single-use
products and menstrual cups ( Figure
). The highest ATBC concentrations were found in sanitary
pads (range: 2714–11314 ng/g) and panty liners (range: <
LOD-13563). ATBC is a popular alternative to DEHP and is currently
widely used as plasticizer in various applications, including medical
devices, cosmetics, and food packaging. Therefore, its widespread detection at high concentrations in plastic-based
menstrual products is perhaps not surprising. In textile-based menstrual
products, ATBC was detected only in one reusable sanitary pad, and
the dominant AP was DEHA, which was detected in all samples of these
products. DEHA concentrations ranged between 71.3 and 1663 ng/g in
reusable sanitary pads and 148–1926 ng/g in menstrual underwear.
DEHA was also detected in some samples of sanitary pads and menstrual
cups but at lower concentrations ( Table S10 ). DEHA is another popular AP with various applications, including
textile materials. DINCH, detected in
a few single-use products, was detected in all TPE menstrual cups
and not in the silicone ones ( Figure S4 ). DINCH is a plasticizer used to produce flexible plastic articles, and this might explain its presence in TPE cups,
which need to be flexible to ensure functionality.
To
estimate the contribution of dermal contact with menstrual products
to plastic additive exposure, the EDIs for the different product types
were calculated ( Table
).
The highest EDIs were
observed for the youngest age group since
the average body weight is the lowest for this group. Looking at the
different types of products, the highest EDIs were observed for single-use
sanitary pads, and the lowest were observed for menstrual cups for
all classes of additives. While some reusable products had higher
PAEs and OPEs concentrations than single-use products ( Figure
), the EDIs for these additives
in reusable products were lower than in single-use products. This
is due to the different use habits. An individual who menstruates
will use approximately 6 single-use sanitary pads during a day, and
in this study, the worst-case scenario (100% of the additive in the
product is released to the skin) was assumed. For reusable products,
the worst-case scenario assumption was similar, but it was considered
that each product will release 100% of the additives through its entire
life cycle. This was achieved by introducing in the EDI formula denominator
( eq
) the number of
uses for an individual product and therefore assuming that the plastic
additives in reusable products will be released in a constant amount
at each use. This is an assumption that might not reflect real-life
situations since part of the chemicals will be released during the
cleaning of these products between uses. Additionally, the release
of plastic additives might change at different stages of use of the
products. It has been shown that the highest amounts of microfibers
are released from clothes during the first 1–4 washes.
,
This might also be the case for plastic additives. Additionally,
the abrasion of reusable menstrual product fibers during washing might
also influence the release of these chemicals from the product to
the skin.
When dermal contact with menstrual products was compared
to other
exposure routes, it was observed that the use of some menstrual products
might contribute significantly to human exposure to plastic additives.
Starting from PAEs, mean EDIs for sanitary pads ( Table
) were comparable to those for
exposure through the diet, which is considered the main route of exposure
to these compounds.
−
Mean EDIs for dietary intake vary between 104 and 13000 ng/kg bw/day
for DEHP
, , −
and 212–61000 ng/kg bw/day for DiNP.
, ,
Mean EDIs for reusable sanitary pads were
comparable to the lowest estimates reported in the literature for
dust ingestion, another major PAEs exposure route (range: 99 and 3980
ng/kg bw/day
−
). EDIs for PAEs in panty liners, tampons, and menstrual
underwear were of the same order of magnitude of the lowest estimates
for air inhalation (range: 6.35–360 ng/kg bw/day
, , ,
) and dermal exposure measured with skin wipes (range:10–1220
ng/kg bw/day
, ,
). Only for menstrual cups were ∑ PAEs EDIs well below estimates
for other exposure routes. Considering the OPEs, the highest mean
EDIs were observed for sanitary pads. The mean EDI for ∑ OPEs
in sanitary pads were higher than those reported for dietary intake
(range: 0.97–103 ng/kg bw/day
, −
), which is considered the main exposure route for OPEs. EDIs for
all other types of products except menstrual cups were comparable
to those reported for ∑ OPEs through other exposure routes,
including air inhalation (range: 1.75–9.2 ng/kg bw/day
−
), dust ingestion (range: 0.07–23 ng/kg bw/day
, ,
), and dermal contact with dust
(range: 5.89–17 ng/kg bw/day
,
). For menstrual
cups, the EDIs for ∑ OPEs were at least 2 orders of magnitude
lower compared to other menstrual products and other exposure routes.
Lastly, for APs, comparison with other exposure routes was more difficult
to realize due to the limited amount of human exposure data for these
compounds. The highest EDIs for APs were observed for sanitary pads,
and these might be comparable to EDIs for dietary intake. Two studies,
including several APs in different food matrices, estimated median
EDIs for ∑ APs through the diet of 244 ng/kg bw/day for adults
living in Spain and of 1515 ng/kg bw/day for adults living in Sweden.
,
Additionally, a recent study, analyzing several APs in plant-based
food collected in Belgium, Germany and the UK, has calculated a mean
EDI for ∑ APs of 610 ng/kg bw/day for a fully vegan diet. However, other studies on food matrices reporting
only few APs found higher EDIs through food consumption (87000 ng/kg
bw/day for DINCH intake through the diet and 30000 ng/kg bw/day for DEHA through soft drink consumption ). EDIs for APs through dermal contact with other
menstrual products, except menstrual cups, were at least 1 order of
magnitude lower than for sanitary pads and were comparable to intake
through other APs exposure routes: inhalation of indoor air (15–358
ng/kg bw/day for ATBC; 6.52–12.1 ng/kg bw/day for TBC) and dust ingestion (2.16–14.4 ng/kg bw/day
for ∑APs).
,
In summary, in many cases,
the EDIs for plastic additives through
dermal contact with menstrual products were comparable to those estimated
for other important exposure pathways. However, it is important to
highlight that the EDI calculations were performed assuming a worst-case
scenario of 100% dermal uptake, which probably differs from a realistic
case. Previous studies measuring the release of chemicals from clothing
found ERFs ranging between 0.06 and 0.75 for OPEs, 0.28–0.98
for PAEs, and 0.33–0.57 for APs.
,
Similar ERFs
values might be expected for menstrual products, especially those
made of textiles, but they might vary depending on the material composition.
Also, AFs for plastic additives are expected to be lower than 1, since
AFs measured these chemicals through regular skin are comprised between
0.13 and 0.75.
,
Noncarcinogenic
risk estimates were well below thresholds for toxicological effects
for all types of menstrual products ( Figure
). The noncarcinogenic risk was negligible
even when the different additives were added together, since the highest
HQ value obtained for the total plastic additives was 1.7 × 10 –2 . The noncarcinogenic risk was negligible for all
3 age groups considered, since the risk estimates for the youngest
age group (highest EDIs due to the lowest body weight) were well below
threshold. On the contrary, for the carcinogenic risk, some products
were above the threshold for cancer effects ( Figure
). However, all carcinogenic risk values
were below 1 × 10 –4 , above which there would
be a high risk. The carcinogenic risk was above threshold for 3 out
10 sanitary pads, 3 out of 8 panty liners, and 2 out of 4 reusable
sanitary pads. The cumulative cancer risk was driven by the presence
of high concentrations of DEHP and DEHA in these products. It is important
to note that this assessment might overestimate the risks for human
health since calculations were based on worst-case scenario estimates
of 100% dermal uptake. Additionally, this assessment has the drawback
that toxicological thresholds used are defined for oral exposure and
not for dermal exposure and this adds additional uncertainties. However,
it is important to highlight that dermal exposure through menstrual
products use is only one of the human exposure pathways to plastic
additives. When added to other exposure pathways (e.g., food or dust
ingestion), the use of menstrual products might contribute to increasing
plastic additives exposure to levels exceeding the thresholds for
human health risks for people who menstruate. Further, it is important
to consider that these products are used during fertile life stages,
and this exposure might be relevant for reproductive health, since
exposure to EDCs is a known risk factor for reproductive effects.
,
Noncarcinogenic
(age group 12–18 years old) and carcinogenic
risk estimates for total plastic additives concentrations in sanitary
pads, panty liners, tampons, reusable sanitary pads, menstrual underwear,
and menstrual cups. The dashed red lines indicate the threshold over
which a risk for human health is considered.
Assuming
a worst-case scenario of 100% release to the environment, the highest
estimates for the release of plastic additives from the use of menstrual
products in Spain were found for single-use products ( Table S18 ). The estimates of the release of plastic
additives to the environment from sanitary pads (median: 225 kg/year;
range 76.9–213127 kg/year), panty liners (median: 82.1 kg/year;
range: 4.96–2039 kg/year), and tampons (median: 472 kg/year;
range: 12.1–1560 kg/year) were at least 1 order of magnitude
higher than for reusable menstrual products. This is due to the higher
number of single-use products consumed and to the high concentrations
of plastic additives found in the packaging of these products ( Table S15 ). Among the reusable products, reusable
sanitary pads (median:7.33 kg/year; range: 1.37–12.5 kg/year)
and menstrual underwear (median: 1.05 kg/year; range: 0.12–1.75
kg/year) showed comparable environmental impact. Menstrual cups were
the products resulting in the lowest release estimates (median: 0.02
kg/year; range: 0.01–0.03 kg/year). Despite the highest release
estimates being found for single-use products, plastic additives release
from reusable products might be more concerning (in particular, from
reusable sanitary pads, which showed the highest plastic additives
concentrations). Single-use products are disposed of as waste directly
after use and are expected to enter a landfill or waste incineration.
For reusable products, the release of plastic additives to the environment
is expected before these products enter the waste cycle, since some
chemicals will be released during their washing between uses. Therefore,
the plastic additives in reusable products might be released to wastewater
and enter the water cycle. This is of concern because wastewater treatment
plants are not always efficient in reducing plastic additives contamination.
Materials
Chemicals and
consumables are listed in Supporting Information .
A total of 41 menstrual
products purchased in 2024 were analyzed. Most products were purchased
from local supermarkets (Barcelona, Spain) and online stores with
national distribution, ensuring that the sampling was representative
of the menstrual products market in Spain. Most brands sampled are
also distributed in EU countries other than Spain, and brands with
an online store provide distribution to other countries within and
outside the EU. Some samples were obtained from products distributed
for free to residents of the Catalan region (Spain) as part of a regional
government health initiative to promote access to reusable menstrual
products. Since these products were obtained
from brands distributed in Spain, these are also considered representative
of the Spanish market. The products selected included single-use (10
sanitary pads, 8 panty liners, and 9 tampons) and reusable (4 reusable
sanitary pads, 4 menstrual underwear, and 6 menstrual cups) products.
This distribution reflects product usage patterns in Spain, where
sanitary pads are the most used (60.6%), followed by panty liners
(49.7%), menstrual cups (48.4%), tampons (42.6%), reusable pads (15.0%),
and menstrual underwear (8.7%). Additionally,
to ensure the sampling was representative of the menstrual products
market, samples for each product type were selected to cover different
brands, product lines (products from the same brand, marketed with
different names because of different properties, like scent and comfort),
sizes, and prices (detailed information in Table S2 ). Brands included were both commercial and private brands
from different supermarket chains, allowing the coverage of a wide
range of price categories. Including products with different costs
(including some distributed for free) supports representativeness
of the sampling, since product cost significantly influences menstrual
product choice due to the widespread problem of menstrual poverty. For the single-use products, the plastic packaging
was also analyzed. Single-use products and packaging were analyzed
separately.
For analysis,
representative portions of each menstrual product were cut into pieces
and weighed in glass tubes to reach a sample weight of 0.1 g. For
sanitary pads, panty liners, reusable sanitary pads, and menstrual
panties, 1 cm 2 squares were cut from different parts of
the products ( Figure S1-a ), always including
all layers (layer in contact with the skin, absorbent layer, and external
layers, which included adhesives in single-use products) to obtain
concentrations representative of the whole product. Tampons, menstrual
cups, and packaging samples were cut in small pieces of approximately
1 cm 3 (tampons and cups) or 1 cm 2 (packaging),
and pieces were randomly selected to achieve the sample amount needed
( Figure S1-b ).
The extraction for
menstrual products and packaging was adapted from a method for plastic
additives in face masks. Briefly, samples
were spiked with 15 μL of 1 ng/μL plastic additives internal
standard mixture ( Table S1 ), left to equilibrate
for at least 2 h, and extracted twice with 40 mL of hexane:acetone
(1:1) using sonication for 15 min. Extracts were filtered with a glass
funnel filled with glass wool to remove large fibers, combined, and
evaporated with a Turbovap evaporator to reach a volume of ∼5
mL. The extracts were transferred to 2 mL vials with Pasteur pipettes
in multiple steps, in which the solvent was gradually evaporated with
nitrogen to allow the transfer of the entire extract. The empty extract
tubes were rinsed with ∼3 mL of clean hexane:acetone to ensure
quantitative transfer. The samples were then evaporated to incipient
dryness using a gentle flow of nitrogen, and 500 μL of methanol
was added. Samples were filtered with a PTFE 0.2 μm syringe
filter and stored at −20 °C until analysis. Plastic additives
were analyzed using an ultrahigh pressure liquid chromatography triple-quadrupole
mass-spectrometer (UHPLC-MS/MS) with a previously published method (more details in Supporting Information ).
To minimize
blank contamination, the use of plastic labware was avoided using
glassware washed with acetone and ethanol and burnt at 400 °C
for 4 h. Since contamination from plastic additives cannot be completely
avoided, each batch of samples included a method blank (empty extraction
tube). Limits of detection (LODs) were established as the minimum
analyte quantity that produced a signal-to-noise ratio of 3. For samples
above the LOD, the blank concentrations were subtracted. The method
was validated in terms of recovery, sensitivity, and reproducibility
(see SI ). Recoveries were between 53 and
94% for PAEs, 44–83% for OPEs, and 47–105% for APs ( Table S3 ). For some analytes (TEP, TPrP, RDP,
4IPPDPPP, TECP, ATEC, DIPA), recoveries between 40 and 50% were considered
acceptable, since reliable quantification was ensured using a matching
internal standard or a close eluting internal standard for quantification
( Table S1 ). LODs were between 0.72 and
71.9 ng/g for PAEs, 0.06–12.5 ng/g for OPEs, and 0.83–93.4
ng/g for APs ( Table S4 ). The RSDs for the
triplicate recovery experiments were <20% for all analytes except
DBP, for which a higher variability can be expected since this compound
is quantified as the sum of two isomers (DiBP and DnBP) ( Table S3 ). In addition, for sanitary pads, which
present a heterogeneous composition, reproducibility of the method
within the same product and within the same batch was evaluated. The
reproducibility within the same product was <15% and within the
same batch was <25% ( Table S5 ), showing
that the sampling strategy was representative and that no variability
in plastic additives content was to be expected within a product batch.
The concentrations of plastic additives found
in menstrual products were used to calculate the estimated daily intakes
(EDIs) through dermal contact with these products (i.e., the intake
of plastic additives during 1 single day of product use), using eq
, adapted from previous
studies.
, ,
1
E D I ( n g k g b w * d a y ) = [ C ( n g p r o d u c t ) * N ( p r o d u c t d a y ) * ERF ( dimensionless ) * AF ( dimensionless ) ] / [ N U ( dim e n s i o n l e s s ) * B W ( k g b w ) ]
where C is the plastic additive
concentration in ng/product (obtained multiplying the ng/g concentration
by the product weight); N is the number of products
used in 1 day; ERF is the easily releasable fraction, i.e., the fraction
of chemical that is released from a product and reaches the skin;
AF is the absorption factor, i.e., the fraction of chemical that from
the skin surface can be absorbed and reach systemic circulation; NU
is the number of uses for an individual product; and BW is the average
body weight of women living in Spain expressed in kg. Table S6 provides the values used for each parameter.
Given that the average body weight of women varies from menarche until
menopause, EDIs were calculated for 3 different age groups: 12–18
years old, 19–40 years old, and 41–51 years old.
,
Since dermal exposure through menstrual
products is still poorly understood, plastic additives ERFs for menstrual
products and AFs for the vaginal and vulvar tissues are not available
in the literature. Therefore, ERFs and AFs were set to 1 for all plastic
additives, assuming a worst-case scenario of 100% release of the additives
from the menstrual products and 100% absorption through the skin.
For some of the additives included in this study, there are published
ERFs for clothing
,
and AFs for normal skin.
,
However, while using a worst-case scenario assumption introduces
uncertainties, using these ERFs and AFs for menstrual products was
considered inappropriate. ERFs for clothing are unreliable for textile-based
menstrual products, which consist of multiple layers, unlike single-layer
garments. Moreover, for products like sanitary pads, panty liners,
tampons, and menstrual cups, ERFs likely differ due to different material
compositions. Similarly, using AFs for regular skin would underestimate
exposure, as vaginal and vulvar skin show higher absorption, particularly
for low molecular weight compounds. Under
this worst-case scenario assumption, the introduction of the number
of products used in a day ( N ) in eq
is equivalent to assuming 100%
release from each individual product. Zeng et al. observed ERFs between 0.39 and 0.97 from t-shirts in dermal
migration experiments with a contact time of 10 h, and Wang et al. observed ERFs between 0.06 and 0.75 in dermal
migration experiments with a duration of 8 h. Therefore, it is possible
that for some chemicals in menstrual products the ERFs could be close
to 100% during the time that only one product is used (this time ranges
from 4 to 6 h). The NU variable was added to the EDI denominator to
account for the fact that each reusable product will release 100%
of its content of plastic additives over its entire product lifespan
rather than in a single day of use. NU is a dimensionless parameter
equal to 1 for single-use products, while for reusable products NU
was estimated by multiplying the average product lifespan (5 years
for reusable sanitary pads and menstrual underwear, 10 years for menstrual
cups ) by the average number of menstrual
bleeding days in 1 year (50.3 days).
For compounds with established
toxicological thresholds, risk assessment was performed in terms of
noncarcinogenic and carcinogenic effects using established guidelines.
−
Briefly, noncarcinogenic risk was assessed by calculating a hazard
quotient (HQ) for each plastic additive. The HQ was calculated by
dividing the average daily dose (ADD) by the noncancer health reference
dose (RfD), minimal risk level (MRL), or tolerable daily intake (TDI)
( Table S7 ). For those compounds with more
than one toxicological threshold defined, the most conservative value
was chosen. A potential noncarcinogenic risk is considered when the
HQ is higher than 1; otherwise, the risk is considered negligible.
Since the RfDs, MRLs, and TDIs used are derived from chronic exposures,
the ADD had to be calculated for a chronic exposure duration (1 year
or longer). The ADD was calculated with eq
using established guidelines:
2
A D D ( n g k g b w * d a y ) = E D I ( n g k g b w * d a y ) * EF ( d a y y e a r ) * ED ( year ) A T ( d a y )
where EDI is the estimated daily intake ( eq
), EF is the exposure frequency,
ED is the exposure duration, and AT is the averaging time. As mentioned
above, EDI is the intake of plastic additives during 1 single day
of product use. EF is the number of days these products are used in
a year. EF was set to 365 for panty liners (these products can be
used daily), while for all other products (only used during menstruation),
the average menstrual bleeding duration (50.3 days/year) was used.
ED is the time that an individual is exposed to plastic additives
through the use of menstrual products. As for EDIs, ADD calculations
were age-specific due to changes in body weight between menarche and
menopause, and ED was set to the exposure years considered: 7 years
(12–18 years old), 22 years (19–40 years old), and 11
years (41–51 years old). AT is the time over which exposure
is averaged and for noncarcinogenic risk is equal to the ED. Therefore, AT was set to 2190 days (12–18
years old), 8030 days (19–40 years old), and 4015 days (41–51
years old).
Carcinogenic risk was calculated only for carcinogenic
additives
with an available oral slope factor (SFO) ( Table S7 ). Since the SFO represents the incremental cancer risk over
a lifetime, carcinogenic risk was evaluated
by multiplying the lifetime average daily dose (LADD) of a plastic
additive by the specific SFO and by 10 –6 for unit
conversion. If the product is lower than 10 –6 , the
cancer risk is considered negligible; if it is between 10 –6 and 10 –4 , there is a potential cancer risk; and
if it is higher than 10 –4 there is a high-potential
cancer risk. The LADD was calculated using eq
:
3
L A D D ( n g k g b w * d a y ) = ∑ ( E D I a g e i ( n g k g b w * d a y ) * E F a g e i ( d a y y e a r ) * E D a g e i ( year ) ) A T ( d a y )
where EDI is the estimated daily intake ( eq
), EF is the exposure frequency,
ED is the exposure duration, and AT is the averaging time. For carcinogenic
risk, a cumulative dose over a lifetime is considered. Therefore,
exposure at different life stages of a menstruator is summed together,
and AT is set to a lifetime (as established by US EPA guidelines ), using the average life expectancy of women
in Spain in 2024 (86.4 years).
For all chemicals included in this study, the toxicological thresholds
are defined for ingestion and not for dermal uptake since there is
not sufficient data from human and animal studies focusing on this
exposure pathway. Therefore, the present risk assessment has uncertainties
related to extrapolation from oral to dermal exposure.
The
environmental impact was assessed by calculating the plastic additives
emissions from menstrual products used in Spain using eq
:
4
A d d i t i v e s e m i s s i o n s ( k g y e a r ) = [ ( C ( n g p r o d u c t ) + C P ( n g p r o d u c t ) ) * N ( p r o d u c t d a y ) * U F ( d a y s y e a r ) * N W * 10 − 12 ] / [ N U ]
where C is the plastic additive
concentration in ng/product; C
P is the
plastic additive concentration in the single-use products packaging
in ng/product; N is the number of products used in
1 day ( Table S6 ); UF is the number of days
in a year in which the products are used (365 days for panty liners,
50.3 days for the other products only used during menstruation); NW
is the number of women in Spain that menstruate (12,154,865 women
with age between 12, average age of menarche, and 51 years, average
age of menopause, in 2024 ); 10 –12 is the conversion factor from ng to kg; NU is the number of uses
for an individual product ( Table S6 ).
Statistical
analyses were performed using R version 4.3.2 (R Core Team). Prior
to statistics calculations, concentrations below LOD were substituted
with LOD/√2. Differences in concentrations of ∑PAEs,
∑OPEs, ∑APs, and total plastic additives between different
types of menstrual products were assessed using the Kruskal–Wallis
rank sum test and pairwise comparisons with the Wilcoxon rank sum
exact test with correction for multiple testing. Associations between
plastic additives concentrations in the menstrual products and in
the packaging were evaluated using Spearman’s rank correlation
coefficients only for those compounds with a detection frequency ≥
50% in both products and packaging (TNBP, ATBC, and TBC). Statistical
significance was set at p < 0.05.
Implications
This study detected a
wide range
of plastic additives, including
PAEs, OPEs, and APs, in both single-use and reusable menstrual products.
While PAEs have been previously reported in single-use products,
−
this is the first study to detect them in reusable products. Moreover,
we report for the first time the presence of OPEs and APs in menstrual
products, which had not been investigated until now. Since more than
13.000 plastic additives exist, it is
to be expected that more of these chemicals might be in use in these
products. In many menstrual products, APs were the dominant additives,
reflecting their widespread use. However, despite their growing use
in consumer products, information about human exposure to these chemicals
is still scarce, and more information about their toxicological properties
is needed.
The EDIs presented in this study show that the dermal
contact with
menstrual products might be a significant exposure pathway. This is
of concern for the health of people who menstruate, as they are already
exposed to PAEs, OPEs, and APs through other routes (e.g.; diet, air
inhalation). As a consequence, people who menstruate might suffer
higher cumulative exposure to these additives, increasing their vulnerability
to the associated health effects. However, these calculations were
based on a worst-case scenario that probably does not reflect real-life
situations. The main factor hindering the calculation of realistic
estimates is the lack of knowledge about dermal exposure. To better
understand dermal exposure through menstrual products, it is important
to test the release of plastic additives from these products under
realistic conditions. The release of some of these chemicals from
other types of consumer products, such as clothing or other fabric
products, has been tested using migration experiments with sweat and
sebum to simulate the surface layer of the skin.
,
These migration assays should be adapted to menstrual products to
also study the effects of vaginal and menstrual fluids on the release
of these chemicals. Additionally, to complete the description of dermal
exposure to plastic additives through menstrual products, AFs for
vaginal and vulvar tissues should be derived. It has been demonstrated
that some plastic additives can be absorbed into the skin. However,
the vulvar and vaginal tissues are known to have a higher absorption
capacity for chemicals, and new models might be needed to measure
absorption through this type of skin. Since the worst-case scenario
estimates showed that some products might be associated with carcinogenic
risks, future studies focusing on the determination of these dermal
exposure parameters are a priority to provide a more realistic risk
assessment.
Another important aspect to consider about the presence
of plastic
additives in menstrual products is the potential environmental impact.
The use of all types of menstrual products might contribute to the
release of plastic additives to the environment through waste disposal
and the washing of reusable products. The highest release of plastic
additives from menstrual products was found for single-use products,
and this was partly due to their packaging, which is directly introduced
in the waste-cycle. Even if the packaging might not contribute significantly
to human exposure, since it is directly disposed, strategies to reduce
the content of chemicals of concern in the packaging as well as to
reduce the packaging amount should be considered to reduce the impact
of these products. However, the chemical content is only a part of
the environmental impact considerations for these products. This information
should complement life cycle assessment studies, considering other
environmental aspects to properly assess the impact of menstrual
products.
Introduction
Menstrual
products are essential for half of the world′s
population to maintain hygiene, prevent infections, provide comfort,
and allow access to educational, occupational, and social activities
during menstruation. However, menstrual
products can contain chemicals of concern for human health, such as
dioxins, pesticides, per- and polyfluoroalkyl substances, and phthalic
acid esters (PAEs).
−
From a human exposure perspective this is a concern, since these
products are used for several days each month from menarche (average
age 12
,
) to menopause (average age 51 ), and the vaginal and vulvar tissues have a
higher chemical absorption capacity compared to other skin tissues. Additionally, these products are used during
fertile life stages, which can be a sensitive time frame for human
exposure, since exposure to endocrine-disrupting chemicals (EDCs)
can be relevant for gynecological and reproductive conditions, such
as endometriosis, adenomyosis, and uterine fibroids.
,
Among the chemicals of concern found in menstrual products
there
are PAEs,
−
,
a group of plastic additives
including chemicals classified as EDCs.
,
Exposure to
some PAEs, like the bis(2-ethylhexyl) phthalate (DEHP), has also been
associated with increasing risk of cancer. Due to these concerns, some PAEs have been regulated in several
countries. In particular, since 2020,
the European Union limited the use of 4 PAEs, including DEHP, dibutyl
phthalate (DnBP), diisobutyl phthalate (DiBP), and benzyl butyl phthalate
(BBzP), in consumer products,
,
to concentrations below
0.1% by weight in plasticized materials. These regulations have been shown to be effective in reducing human
exposure to these chemicals.
−
However, PAEs are still widely used in products, and high molecular
weight PAEs, like the diisononyl phthalate (DiNP) and the diisodecyl
phthalate (DiDP), have emerged as alternatives to the regulated ones,
even if these substances are also showing associations with potential
adverse effects.
Despite the detection
of high concentrations of PAEs in menstrual
products, data on the occurrence of other plastic additives are lacking.
Among plastic additives, two additional classes of interest for human
exposure are organophosphate esters (OPEs) and alternative plasticizers
(APs). These two classes of plastic additives have been previously
detected in consumer products (face-masks, textiles, and food contact materials ) but have not been analyzed in menstrual products,
so far. The presence of OPEs in consumer products is a concern because
these compounds have been linked to various health effects, including
immunotoxicity, neurotoxicity, and endocrine disruption. Additionally, chlorinated OPEs, like tris(2-chloroethyl)
phosphate (TCEP) and tris(2-chloroisopropyl) phosphate (TCIPP), have
been classified as carcinogenic. APs
include a variety of novel plasticizers, such as citrates, adipates,
and trimellitates, which have become widely used as a response to
the toxicological concerns surrounding OPEs and PAEs.
,
However, information about APs toxicological properties is still
scarce, and recent studies are showing that some of these chemicals
can also be linked to adverse effects. For example, acetyl tributyl
citrate (ATBC) and tri- n -butyl citrate (TBC) showed
neurotoxic effects in animal studies and ATBC, diisononyl cyclohexane-1,2-dicarboxylate
(DINCH), and di(2-ethylhexyl) (DEHA) have shown potential thyroid
disruption.
,
The goals of the present
study were (1) to investigate the occurrence
of 3 classes of plastic additives, including PAEs and, for the first
time, OPEs and APs in different types of single-use and reusable menstrual
products; (2) to assess the contribution of dermal contact with these
products to plastic additives human exposure; (3) to evaluate the
human health and environmental impacts associated with the use of
different menstrual products.
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