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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.