are sunscreen uv filters polluting our beaches? a case
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HAL Id: hal-03373825https://hal.archives-ouvertes.fr/hal-03373825
Submitted on 11 Oct 2021
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Are sunscreen UV filters polluting our beaches? A casestudy from consumer habits to water analysis on the
French Mediterranan Coast CoauthorsJérôme Labille, Danielle L. Slomberg, Riccardo Catalano, Olivier Radakovitch,
Samuel Robert, Marie-Laure Trémélo, Jean Luc Boudenne, Manasfi Tarik
To cite this version:Jérôme Labille, Danielle L. Slomberg, Riccardo Catalano, Olivier Radakovitch, Samuel Robert, etal.. Are sunscreen UV filters polluting our beaches? A case study from consumer habits to wateranalysis on the French Mediterranan Coast Coauthors. International Symposium of LabEx DRIIHM,Sep 2021, Toulouse, France. 2021, �10.34972/driihm-12a97c�. �hal-03373825�
Are sunscreen UV filters polluting our beaches? A case study from consumer habits to water analysis on the French Mediterranan Coast
Coauthors:Jérôme Labille, Danielle Slomberg, Riccardo Catalano, Olivier Radakovitch
Aix-Marseille Université / CNRS, CEREGE, UMR 7330, Aix en Provence, France
Samuel Robert, Marie-Laure Apers-TréméloAix-Marseille Université / CNRS, ESPACE, UMR 7300, Aix-en-Provence, France
Jean-Luc Boudenne, Tarik ManasfiAix-Marseille Université / Laboratoire Chimie de l’Environnement, UMR 7376, Marseille, France
UV filter i %UVi mUVi /g PEC UVi / g/L CUVi / g/L /% recovery
TiO2 col 17 251
46 21 45.5
TiO2 tsl 5,300 117-895 16.8
ZnO col 3 44
8 2.4 13.4
ZnO tsl 938 11 0.6
AVO col 80 1,181
217 0.3 0.14
AVO tsl 25,000 0.015-0.048 0
OC col 57 842
154 0.03 0.02
OC tsl 17,800 0.04-0.14 0
OMC col 17 251
46 0 0
OMC tsl 5,300 0 0
OXY col 2 30
5 0.015 0.28
OXY tsl 625 0.038-0.05 0.01
Predicted environmental concentrations of UV filters and actual recovery
Two distinct scenarios found for the mineral and organic !lters. While up to 45% of the mineral !lters used by beachgoers may be released into the seawater, the organic !lters were minimally recovered in the environment, most likely due to internalization through the skin barrier or partial photodegradation.
"ux of the suncare product consumed and potentially transferred to the bathing water
total number of people attending the beach
average number of times the product is applied to the skin per visit to the beach
mass of product consumed during each application to the entire body
% of people that reported using suncare products before bathing
= 52.5 ± 16.5 kg / day = 367 ± 114 kg / week = 1.45 ± 0.45 t / month
mass of UV !lter i involved
occurrence of the UV !lter i within the panel of suncare product compositions used
average mass fraction of the UV !lter i used in the product formulation (6.5 %)
PECUVi = mUVi / Vpredicted environmental concentration
for the UV !lter i in the bathing water
volume of bathing water= 5,400 m3 for Prophète Beach water column
= 47 m3 for top surface layer
Mass of UV !lters consumed and potentially entering the bathing water, in g/day:- organic UV !lter > 1 kg/d- ZnO and TiO2 = 83 and 633 g/d - cumulated UV !lters = 15.7 kg/dThis quantity of UV !lters may be released or remain on the skin, depending on the retention factor.These values account for a beach daily attendance of 3,000 people.
Methodological approachFrom the mass of UV !lter consumed on the beach recovered from our surevey, we calculated a predicted environmental concentration in the bathing water, PECUVi as follows.
%
Yes Yes Yes
No No No
0
20
40
60
80
100
La Lave Pointe Rouge Prophète
resp
onde
nt %
Do you usually use a suncare product? If yes, do you apply it to ?
whole body,
80
upper body,
15
face only, 4
Social Survey
Beachgoer habits regarding bathing activity at the beach
Suncare product consumption habits on the beach
78 62
56 52
40 31
20 19
17 14
9 9
8 3
2 2
18
19 2
5
0 10 20 30 40 50 60 70 80
Avobenzone - UVA Bemotrizinol - UVB + UVA
Octocrylene - UVB + short UVA Octisalate - UVB
Ethylhexyl triazone - UVB Homosalate - UVB
Iscotrizinol - UVB + short UVA Drometrizol trisiloxane - UVB + short UVA
Octinoxate - UVB Ecamsule - UVA
Diethylamino hydroxybenzoyl hexyl benzoate - Bisoctrizole - UVB + UVA
Ensulizole - UVB Padimate O - UVB
Bisdisulizole disodium - UVA Oxybenzone - UVB + short UVA
MBBT (nano) - UVB + UVA
TiO2 - UVB + short UVA ZnO - UVB + UVA
no UV protection
UV filter occurrence (%)
TiO2 78%, TiO2 (nano) 61% ZnO 33%, ZnO (nano) 66%
no UV filter inside mineral UV filters organic UV filters of nano size organic UV filters
UV !lter occurrence among the suncare products used on the three beaches Data recovered from 124 photographies of products. Speci!c UV absorption range of each !lter is given as /!lter name – UV range/. For mineral UV !lters, the occurrence of non-nano and nano forms are given; an overlap exists for TiO2 when both forms are labeled on products
14
12
43
15
17 NA
others
dilution effect
product is adapted
no relation 37
12 13
28
5 NA
others
probably not good
washes off with bath
bad for fauna and flora
pollution
cream composition
Yes, 66.3 No, 14.0
I don't know, 19.3
NA
no SPF 4%
SPF 4 - 10 6%
SPF 15 - 20 13%
SPF 30 27% SPF 50
12%
SPF 50+ 35%
nd 3% Garnier Ambre
solaire. 14%
Nivea Sun. 13%
Avène. 12%
La Roche Posay. 9% Bioderma. 7%
L'Oréal. 6%
Soleil noir. 3%
Yves Rocher. 3%
Vichy. 3%
Corine de Farme. 2%
Lovea. 2%
Soleil Biafine. 2%
Mixa solaire. 2%
Nuxe sun. 2%
other brands < 1.2%. 20%
73 18
16 12
7 5
3 7
9 2
SPF texture, odor
brand composition
cost water resistance
tan other criteria
no criteria no answer
!"#$%&'(
!"#$%&)(
!"#$%&*(
!"#$%&+(
!"#$%&'(
!"#$%&)(
!"#$%&*(
!"#$%&+(
environment impact, 3 consumer health, 19
BIO label, 22
no detail, 57
Cosmetic brands providing the suncare products used on the beach
Solar protection factors of the suncare products used on the beach
What are your three primary criteria for selecting a suncare product?
Do you think that suncare products can impact the quality of marine bath water?
0 20 40 60 80
never
seldom
frequently
everytime
La Lave Prophète Pointe Rouge 12 9 16
41 58 51
37 30 29
La Lave Pointe Rouge Prophète
NA > 4 times 2 - 3 times 1 time
86 91 92
La Lave Pointe Rouge Prophète
NA no yes
How often do you practice bathing? If yes, how many times do you bathe per visit?
Do you practice whole body immersion?
68% of beachgoers use sunscreen 2.6 times per visit to the beach.
3,000 beachgoers/day = 52.5 kg sunscreen applied by bathers = 15.7 kg UV !lter potentially released
No use of suncare products labeled as eco-friendly, despite consumer awareness
More than 75% of the 471 interviewees bathe every time they go to the beach.
Discrepancy between the claimed awareness regarding the environmental impact of suncare products and the quasi-total absence of any product labeled as eco-friendly among those actually consumed (only 2 out of 170 products).
Sun protection factor (SPF) is the p a r a m o u n t consideration in selecting and buying a suncare product, with clear majority of medium and high SPF.
Composition is the criteria number 4.
Local suncare product consumption is dominated by only 5 well-known brands.
Methodological approachWe assessed beach attendance through user counts and photographic images. Simultaneously, a questionnaire was carried out on-site between 8:00 am and 8:00 pm. We surveyed 471 people. Beachgoers were asked speci!c questions about their sunscreen use (type, frequency, and time of application) and their opinion regarding the possible e#ects of these products on the marine environment.The containers of the suncare products used by the interviewees were photographed and the information on the packaging, such as brand, SPF, and composition were recorded. A total of 124 suncare product compositions were reported.
This enabled us to estimate the average composition and maximum UV !lter (i.e., organic and mineral) quantity that could be released daily into the beach water.
Field localisation, Marseille, Mediterranean coast, France
Sampling points on the three beaches studied
Time evolution of organic UV !lter concentrations at the three distances from shore line at Prophète Beach Concentrations in water column (col) are compared to those in the top surface layer (tsl).
UV filter quantification in bathing water
Concentrations of Ti and Zn found in di"erent water fractions during peak attendance
50 m OMC50m DIOXY200m OC200 m AVO200 m OXY200 m OMC200m DIOXY
40cm surftop surface layer
40 cm depth
OC
AV
OO
XY
OM
CD
IOX
YO
C A
VO
OX
YO
MC
DIO
XY
OC
AV
OO
XY
OM
CD
IOX
Y
0
50
100
150
200
250
300
350
400
450
OC
AV
OO
XY
OM
CD
IOX
YO
CA
VO
OX
YO
MC
DIO
XY
OC
AV
OO
XY
OM
CD
IOX
Y
0
50
100
150
200
250
300
350
400
450
OC
AV
OO
XY
OM
CD
IOX
YO
CA
VO
OX
YO
MC
DIO
XY
OC
AV
OO
XY
OM
CD
IOX
Y
0
50
100
150
200
250
300
350
400
450La Lave Prophète Pointe Rouge
BZ1 BZ2 BBZ BZ1 BZ2 BBZ BZ1 BZ2 BBZ
Concentrations of organic UV !lters (ng/L) OC, AVO, OXY, OMC, and DIOXY found in di"erent water fractions during peak attendance
0
20
40
60
80
100
120
0
20
40
60
80
100
120
0
5
10
15
0
5
10
15
0
5
10
15
A
B
Con
cent
ratio
n Ti
(µg/
L)
Con
cent
ratio
n Zn
(µg/
L)
BZ1 BZ2 BBZ
0.02to0.50.5surfacetop surface layer > 0.5 µm 0.02 < x < 0.5 µm
La Lave Prophète Pointe Rouge
water column
0
20
40
60
80
100
120
0
20
40
60
80
500
520
540
BZ1 BZ2 BBZ BZ1 BZ2 BBZ
During the peak recreational time, mineral UV !lters were detected in:- higher concentrations in the bathing area than o#shore,- higher concentration in top surface layer than in the water column:
in tsl and col respectively: TiO2: 100-900 > 20-50 µg/LZnO: 10-15 > 1-3 µg/L
Methodological approachOn Saturday, July 15th, 2017, water samples were collected at 4:00 pm, during peak recreational activity. The spatial distribution of any UV !lters in the waters was assessed by sampling at three distances from the shoreline in Bathing Zone 1 (BZ1), Bathing Zone 2 (BZ2) and beyond the Bathing zone (BBZ). Water samples were collected at two depths:- the top surface layer (tsl) (~ 1 cm), where hydrophobic compounds would likely be concentrated;- 40 cm was selected as a constant sampling depth to represent the average water column (col).Additional samplings were conducted at 8:00 am on Saturday, July 15 and Sunday, July 16, 2017, i.e. just before and after the studied peak attendance.
Mineral UV !lter quanti!cation: After digestion, quadrupole ICP-MS was used to analyse Ti and Zn concentrations as indicators of mineral UV !lters. local geochemical background was acounted from the concentrations recovered beyond the bathing zone (BBZ).
Organic UV !lters quanti!cation: dioxybenzone (DIOXY), oxybenzone (OXY), avobenzone (AVO), 2-ethylhexyl-4- methoxycinnamate (OMC), and octocrylene (OC) were analysed using liquid chromatographic/mass spectrometry.
During the peak recreational time, organic UV !lters were detected in:- higher concentrations in the bathing area than o#shore,- higher concentration in top surface layer than in the water column:
OC: 40-420 > 30-150 ng/LAVO: 10-15 > 10-350 ng/L
The three UV !lters are found in the water column only in the bathing zone and during recreational activity.
This trend was not observed in the top surface layer (tsl), where residence time must be shorter.
In order to assess the release of UV !lters from the sunscreen used by beachgoers into seawater within the bathing zone, a !eld campaign was carried out during the summer of 2017 at three beaches in Marseille, along the French Mediterranean coast. A social survey analyzed beachgoer attendance, the quantities and types of suncare products used and the bathing frequencies, while the bathing water was analyzed spatially and temporally so as to quantify both mineral and organic UV !lters directly released and recovered.During the peak recreational time at the three beaches, both mineral and organic UV !lters were detected in higher concentrations in the bathing area than o#shore. In general, higher concentrations were recovered in the water top surface layer than in the water column, giving respectively 100-900 and 20-50 µg/L for TiO2, 10-15 and 1-3 µg/L for ZnO, 40-420 and 30-150 ng/L for octocrylene, and 10-15 and 10-350 ng/L for avobenzone. More than 75% of the 471 interviewees reported bathing every time they go to the beach, with 68% using a suncare product 2.6 times on average. From these data we estimated that an average mass of 52 kg/day or 1.4 t/month of suncare products are possibly released into bathing water for a beach attended by 3,000 people daily. The mass ratio of UV !lters in such products typically ranges from 0.03 to 0.1, allowing us to propose theoretical maximum concentrations in the beach water. Our recovery of measured UV !lter concentrations in seawater compared to the theoretical concentrations revealed two distinct scenarios for the mineral and organic !lters. While up to 45% of the mineral !lters used by beachgoers may be released into the seawater, the organic !lters were minimally recovered in the environment, most likely due to internalization through the skin barrier or partial photodegradation.
Abstract
Aims of this work - to estimate the daily "ux of sunscreen and UV !lters transferred from beachgoers into the bathing water on a standard summer day; - to study the possible co-occurrence of organic and mineral UV !lters in seawater, both in the water top surface layer and water column; - to determine, for the !rst time, the patterns of UV !lter occurrence in the bathing water at three French Mediterranean beaches. This study is the !rst !eld campaign coupling chemical water analysis to quantify both organic and mineral UV !lters in seawater, with a simultaneous social survey of consumer’s habits on the beach.
TiO2 ( g/L)
AVO (ng/L)
top surface layer
900 0.3
water column 20 0.05
recovery %
17-45
0-0.1 0
2 4 6 8 10 12
BZ1 BZ2
BBZ
Ti (Ɋg/L)
OK NO
Daily: 3,000 beachgoers = 52.5 kg sunscreen applied by bathers = 15.7 kg UV-filter possibly released
Sunscren Use
Swim
Soil Fresh water - Seawater Landfill
leachates clear water sludg
e
Wash
Disposal
Waste
WWTP
solids
Scenarios of UV !lter release to the water usage cycleAmong the variety of scenarios of environmental release, this work deals the direct release via recreational activities.
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