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Most current bioexposure assessments for UV filters focus on contaminants concentrations in fish from river and lake. To date there is not information available on the occurrence of UV filters in marine mammals. This is the first study to investigate the presence of sunscreen agents in tissue liver of Franciscana dolphin (Pontoporia blainvillei), a species under special measures for conservation. Fifty six liver tissue samples were taken from dead individuals accidentally caught or found stranded along the Brazilian coastal area (six States). The extensively used octocrylene (2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate, OCT) was frequently found in the samples investigated (21 out of 56) at concentrations in the range 89-782 ng.g-1 lipid weight. São Paulo was found to be the most polluted area (70% frequency of detection). Nevertheless, the highest concentration was observed in the dolphins from Rio Grande do Sul (42% frequency of detection within that area). These findings constitute the first data reported on the occurrence of UV filters in marine mammals worldwide.
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First Determination of UV Filters in Marine Mammals. Octocrylene
Levels in Franciscana Dolphins
Pablo Gago-Ferrero,
Mariana B. Alonso,
Carolina P. Bertozzi,
Juliana Marigo,
Lupércio Barbosa,
Marta Cremer,
Eduardo R. Secchi,
Alexandre Azevedo,
JoséLailson-Brito Jr.,
Joao P. M. Torres,
Olaf Malm,
Ethel Eljarrat,
M. Silvia Díaz-Cruz,*
and DamiàBarceló
Department of Environmental Chemistry, Water and Soil Quality Research Group, IDAEA-CSIC, Jordi Girona 18-26, 08034
Barcelona, Spain
Projeto BioPesca, R. Paraguai, 241. Praia Grande, SP, Brasil, 11702-070.
Laboratory of Radioisotopes - Biophysics Institute (UFRJ), Av. Carlos Chagas Filho, 373 CCS - Bl. G, Rio de Janeiro, RJ, Brasil,
Laboratory of Aquatic Mammals and Bioindicators (UERJ), R. São Francisco Xavier, 524 - S.4018 - Bl. E, Rio de Janeiro, RJ, Brasil,
Instituto ORCA, Vila Velha, ES, Brasil
Universidade de Joinvile (Univille), Joinvile, SC, Brasil
Laboratory of Turtles and Marine Mammals (FURG), Rio Grande, RS, Brasil
Catalan Institute for Water Research (ICRA), Scientic and Technological Parc of the University of Girona, Emili Grahit, 101 Edici
H2O, 17003 Girona, Spain
ABSTRACT: Most current bioexposure assessments for UV
lters focus on contaminants concentrations in sh from river
and lake. To date there is not information available on the
occurrence of UV lters in marine mammals. This is the rst
study to investigate the presence of sunscreen agents in tissue
liver of Franciscana dolphin (Pontoporia blainvillei), a species
under special measures for conservation. Fifty six liver tissue
samples were taken from dead individuals accidentally caught
or found stranded along the Brazilian coastal area (six states).
The extensively used octocrylene (2-ethylhexyl-2-cyano-3,3-
diphenyl-2-propenoate, OCT) was frequently found in the
samples investigated (21 out of 56) at concentrations in the
range 89782 ng·g1lipid weight. São Paulo was found to be
the most polluted area (70% frequency of detection). Nevertheless, the highest concentration was observed in the dolphins from
Rio Grande do Sul (42% frequency of detection within that area). These ndings constitute the rst data reported on the
occurrence of UV lters in marine mammals worldwide.
UV lters (UV F) are emerging environmental contaminants
for which there is currently a lack of knowledge about their
occurrence, fate, and eects on the ecosystems.
constitutes a large and heterogeneous group of chemicals that
are ingredients in personal care products to protect skin and
hair from the sunlight, and in other industrial goods such as
paint, wax, plastic, or textile to prevent photodegradation of
polymers and pigments.
These chemicals enter the aquatic environment either
indirectly, via wastewater treatment plant euents (urban and
industrial) or directly, through human aquatic recreational
activities. Previous studies have demonstrated the occurrence of
UV F in water, sewage sludge, sediment, and biota.
UV F are lipophilic compounds, therefore have the potential for
bioaccumulation and biomagnication in aquatic ecosystems
through the trophic chain.
Works on biota were mainly
focused on sh,
but other organisms have been studied as
well, such as sh eating birds and aquatic invertebrates.
UV lters are known to have toxic eects on both aquatic and
terrestrial organisms. Although the studies dealing with
ecotoxicity of these compounds is scarce, they have been
shown to act as environmental estrogens and antiandrogens,
cause reproductive disruption and aect the thyroid axis.
far, there is still even more limited information available about
Received: February 14, 2013
Revised: April 19, 2013
Accepted: April 29, 2013
Published: April 29, 2013
© 2013 American Chemical Society 5619 |Environ. Sci. Technol. 2013, 47, 56195625
the fate and eects of these chemicals in marine ecosystems.
High levels of multiclass UV F in seawater have been reported,
with concentrations up to 799 ngL1of 4-methylbenzylidene
camphor (4MBC).
Recently, it has been documented that
UV F caused harmful eects on coral reefs (coral bleaching) by
promoting viral infections.
As regards marine biota, the
analysis of four benzotriazole UV stabilizers, namely UV-320,
UV-326, UV-327, and UV-328, and the UV lter 4MBC in
marine organisms from the Ariake Sea (Japan) revealed that the
three benzotriazole stabilizers investigated bioaccumulated in all
the species analyzed, from benthic invertebrates to several sh
species, including the hammerhead shark.
Among UV lters, octocrylene (2-ethylhexyl-2-cyano-3,3-
diphenyl-2-propenoate, OCT) is of great concern since it is a
highly lipophilic compound (log Kow 6.88), stable, and resistant
to sunlight degradation, but there is evidence that it can trigger
the production of potentially harmful free radicals (reactive
oxygen species) when it releases the absorbed energy. The
widespread occurrence of this compound, as well as its high
concentrations found in sewage sludge and sediments
appears to be associated with its extensive use in formulations,
especially personal care products, because both protects in
UVA and UVB regions, and augments the absorbing capacity of
other organic UV lters, such as ethylhexylmethoxycinnamate
(EHMC), avobenzone (AVB), and benzophenone-3 (BP3).
Since maintaining the absorption capacity is important to
prevent erythema and to reduce the subsequent risk of
melanoma development, formulations containing OCT had
superior performance compared to other formulations that did
not contain OCT, and therefore, preferably used.
The goal of the present study was to contribute for a better
understanding of the impact of the increasing use of UV lters
in densely populated coastal areas on marine organisms. The
study aimed at demonstrating the potential for biomagnication
of the extensively used sunscreen agent OCT on marine
mammals, specically on dolphin, since they occupy a higher
trophic level in the marine food chain, and have relatively low
metabolic activity, thus accumulating high levels of organic
pollutants in their body.
For this study Franciscana dolphin
(Pontoporia blainvillei) was the selected species. It is a small
cetacean with a distribution restricted to the southwest Atlantic
Ocean. This is the most impacted cetacean othe eastern coast
of South America
and is listed as vulnerablein the Red
Book of the International Union for Conservation of the
Nature (IUCN). Franciscana was considered a species that
needs particularly measures of conservation
and is also
included in the Index II of the Convention on International
Trade in Endangered Species of Wild Fauna and Flora, that
Argentina, Uruguay, and Brazil are undersigned. Their coastal
distribution makes it particularly vulnerable to human activities
such as incidental capture in sheries and habitat degradation
by anthropic contaminants.
Evidences suggest that the
mortality rates are excessive and unsustainable.
Chemicals and Reagents. OCT (>98% purity), and the
isotopically labeled compound benzophenone-d10 (BP-d10 99%
purity), used as internal standard (IS), were obtained from
Sigma-Aldrich (Steinheim, Germany). Organic solvents and
HPLC grade water (Lichrosolv), as well as H2SO4, formic acid
(98% purity) and hydromatrix were provided by Merck
(Darmstad, Germany). Nitrogen and argon (purchased from
Air Liquid, Barcelona, Spain) were of 99.995% purity. The
syringe and the pressurized liquid extraction (PLE) cellulose
lters used were purchased from Whatman (London, U.K.) and
from Dionex Corporation (Sunnyvale, CA), respectively.
Isolute Alumina Cartridges used for solid phase extraction
(SPE) were obtained from Biotage (Uppsala, Sweden).
The OCT and BP-d10 stock standard solutions were prepared
in methanol at 200 mg L1. The solutions were stored in the
dark at 20 °C. A diluted 20 mg L1stock standard solution
was prepared weekly. Working solutions were prepared daily by
appropriate dilution of the diluted stock standard solution.
Sampling Area and Sample Collection. The Brazilian
coastline has around 8500 km of length. The Southeast
Brazilian region, historically, had turned into an important
industrial center of Brazil. Rio de Janeiro and São Paulo States
are the most anthropogenically disturbed areas along the
country shoreline. Massive metropolitan complex surrounds the
estuaries and bays, which have been receiving discharges of
chemical contaminants from domestic, industrial and agricul-
tural wastewaters besides also they are impacted by overshing,
harbor activities, and solid trash.
Santos estuary, in São
Paulo coast, is the most important Brazilian example of
environmental degradation from aquatic and atmospheric
pollution by industrial origin. The largest harbor in Latin
America (the Port of Santos) and the largest industrial complex
in Brazil are located in this area. Industrial activities began in
the 1950s with the establishment of diverse factories (steel, oil,
and agribusiness) and have turned this estuary into the nal
destination for toxic waste and contaminated euents since
See Figure 1 for a map of the study areas.
Collected samples were taken from individual dolphins found
stranded dead at the beaches or incidental caught in shing nets
along the Brazilian coast, Southwestern Atlantic, from 1994 to
2009. Available information on the samples is given in Table 1.
Sexual maturity is known to occur at dierent length depending
on the coastal area. The individuals considered in this study
included males and females, adult (sexually matured), juvenile
(sexually immature >100 cm length) and calves (sexually
immature <100 cm length) specimens.
Figure 1. Study area map, Southeaster and Southern coast of Brazil.
Brazilian States sampled: ES, Espi ́
rito Santo; RJ, Rio de Janeiro; SP,
São Paulo PR, Paraná; SC, Santa Catarina; RS, Rio Grande do Sul;
FMA, Franciscana Management Areas (IIV).
Environmental Science & Technology Article |Environ. Sci. Technol. 2013, 47, 561956255620
Table 1. Sampling Locations and Dates, Biological Information on the Dolphins Collected along the Brazilian Coast, And
Concentrations of OCT in the Liver Samples
location Brazilian State sample code sex length sexual maturity physical maturity sampling date (year) concentration OCT (ng g1lw)
Espirito Santo (12) FT: 25% PON 08 M 70 Im Ca 20032006 nd
PON 12 M 73 Im Ca 20032006 129
PON 11 M 100 Im Ju 20032006 nd
PON 02 M 112 Im Ju 20032006 nd
PON 13 M 113 Im Ju 20032006 nd
PON 06 M 114 Im Ju 20032006 nd
PON 14 M 115 Ma Ad 20032006 nd
PON 09 M 117 Ma Ad 20032006 nd
PON 07 F 109 Im Ju 20032006 nd
PON 15 F 115 Im Ju 20032006 nd
PON 03 F 118 Im Ju 20032006 89
PON 10 F 136 Ma Ad 20032006 712
Rio de Janeiro (1) FT: 0% FT: 0% RJ 46 uk na na na 20032006 nd
Sao Paulo (10) FT: 70% BP 125 M 100 Im Ju 2006 100
BP 120 M 103 Im Ju 2005 nd
BP 133 M 112 Ma Ad 2006 380
BP 149 M 116 Ma Ad 2007 144
BP 176 M 122 Ma Ad 2008 141
BP 110 M 124 Ma Ad 2006 nd
BP 108 F 94 Im Ca 2006 524
BP 113 F 110 Im Ju 2006 269
BP 151 F 138 Ma Ad 2007 130
BP 140 F 110 Im Ju 2006 nd
Paraná(3) FT: 33% PR 50 F 56.5 Im Ca 20032006 129
PR 53 F 98 Im Ca 20032006 nd
PR 01 F 140 Ma Ad 20032006 nd
Santa Catarina (11) FT: 18% PB 221 M 83.5 Im Ca 20032006 nd
PB 23 M 102 Im Ju 20032006 nd
PB 22 M 107 Im Ju 20032006 nd
PB 53 M 87.3 Im Ca 20032006 345
PB 62 M102 Im Ju 20032006 401
PB 56 M109 Im Ju 20032006 nd
PB 222 F 129 Ma Ad 20032006 nd
PB 30 F 133 Ma Ad 20032006 nd
PB 37 F 133.5 Ma Ad 20032006 nd
PB 162 uk 127.5 Ma Ad 20032006 nd
PB 44 uk 145 Ma Ad 20032006 nd
Rio Grande do Sul (19) FT: 42% CA 143 M 125.5 na na 1997 nd
CA 32 M 129.5 Ma Ad 1994 nd
CA 142 M 133.7 Ma Ad 1997 nd
CA 36 M 137 Ma Ad 1994 153
CA 156 M 137 Ma Ad 1998 nd
CA 172 M 143 Ma Ad 1999 nd
CA 152 F 107.5 Im Ju 1998 142
CA 63 F 135.5 Im Ju 1994 nd
CA 124 F 137 Im Ju 1997 nd
CA 153 F na na na 1998 nd
CA 33 M 131 Ma Ad 1994 473
CA 108 F 157 Ma Ad 1995 nd
CA 173 F 161 Ma Ad 1999 493
CA 179 M 110 Im Ju 1999 107
CA 193 F 116 Im Ju 1999 129
CA 194 F 123 Im Ju 1999 782
CA 234 M 103 Im Ju 2000 103
CA 237 M 132 Im Ju 2000 nd
Environmental Science & Technology Article |Environ. Sci. Technol. 2013, 47, 561956255621
Fifty six individual were analyzed, belonging to many States
of Brazil: Espi ́
rito Santo (n= 12), Rio de Janeiro (n= 1), São
Paulo (n= 10), Paraná(n= 3), Santa Catarina (n= 11) and
Rio Grande do Sul (n= 19). Liver samples collected were
placed in aluminum foil, frozen, and further lyophilized. Freeze-
dried liver tissue was ground, homogenized and stored in
brown glass sealed containers at 20 °C until analysis.
Analytical Methods. In order to prevent contamination
and photodegradation of samples and standard solutions all
glassware used was previously washed and heated overnight at
380 °C, and further sequentially rinsed with dierent organic
solvents and HPLC grade water. Separate solvents and only
previously unopened packages of solvents, chemicals and other
supplies were used. In addition, a set of at least two operational
blanks were processed together with each batch of samples.
Standard solutions and samples were always covered with
aluminum foil and stored in the dark. Furthermore, gloves were
worn during the sample preparation process.
Sample Preparation. Ssamples were extracted by PLE using
an automatic extractor ASE 200 (Dionex Corporation,
Sunnyvale, CA, USA). One gram dry weight of freeze-dried
dolphin liver tissue was mixed in the extraction cells with
hydromatrix. The PLE optimized parameters were as follows:
preheating of 5 min, heating of 5 min, two extraction cycles of
10 min using dichloromethane/hexane as extraction solvent (1/
1, v/v), temperature of 100 °C, pressure of 10 000 kPa, ush
volume of 80% of cell and 90 s of nitrogen purge. The PLE
extract obtained was concentrated to 3 mL and then subjected
to a purication step via acid attack with concentrated H2SO4
(9597% purity) (4 ×2 mL). The extract was puried by SPE
with alumina cartridges (5 g/20 mL), using 40 mL of
hexane:dichloromethane (1/2). Finally, the extract was
evaporated to dryness. The residue was further reconstituted
with 0.1 mL of acetonitrile and the IS was added before LC-MS
Lipid Content Determination. The lipid content determi-
nation was performed by gravimetric analysis. After the
extraction, the extracts were concentrated to incipient dryness,
each vial was weighed and the dierence between the initial
weighing and weighing after the addition and evaporation rate
was used to calculate the percentage of lipids.
Percentage lipid content was determined for each individual.
Mean values were calculated for those specimens sampled in
the same geographical area, which were in the range 4% - 7%.
UPLC-ESI(+)-MS/MS Analysis. Target analysis of OCT was
performed by ultrahigh performance liquid chromatography
(UPLC)-tandem mass spectrometry (MS/MS) using an
Acquity UPLC chromatograph attached to a triple quadrupole
detector (TQD) mass spectrometer (Waters). A Hibar
Purospher STAR HR R-18 ec. (50 mm ×2.0 mm, 2 μm)
column (Merck) was used. The solvent ow rate was set to 0.4
mL min1and the column temperature was kept at 50 °C. The
sample volume injected was 10 μL. The chromatographic
separation was performed by using as mobile phase HPLC
grade water (A) and acetonitrile (B), both with 0.3% formic
acid. The adopted elution gradient started with 5% of eluent B,
increasing to 95% in 1.20 min, kept constant for 2.30 min, and
rising to 100% in the following 0.5 min. During the next 2.5
min the elution gradient was kept constant, and then back to
initial conditions in 3 min.
MS/MS was operated in selected reaction monitoring
(SRM) and positive electrospray ionization mode (ESI+).
The optimized parameters were as follows: desolvation gas
(nitrogen), 750 L h1; collision gas (argon), 0.19 mL min1,
nebulization gas (nitrogen), 90 L h1; ion spray voltage 3.35
kV; source temperature, 130 °C and desolvation temperature,
450 °C. Two characteristic transitions of the protonated
molecular ion [M+H]+(precursor ion) were recorded.
For the positive conrmation of OCT in liver tissue samples,
strict criteria had to be met in order to avoid false positives.
Following the European Commission Decision 2002/657/
that although it was initially conceived for food residue
analysis, it has been accepted by the scientic community for
environmental analysis, a minimum of three identication
points (IPs) is required for this purpose. In our case, these 3
IPs corresponded to the precursor ion (m/z362 amu) and to
the two transitions recorded from the precursor ion ([M+H]+)
to the product ions [M+HC8H16]+and [M+HC8H16
H2O]+at m/z250 and 232 amu, respectively. Besides, the
chromatographic retention time of the analyte in the sample
should not vary more than 2.5% in comparison to the
calibration standards, and the relative abundance of the two
SRM transitions monitored must also be compared to the
standardscorresponding values, and range about ±20%. Figure
2 represents the chromatograms for OC corresponding to a
standard solution at 40 ng mL1, and to a dolphin liver sample
from an adult male from São Paulo. In this case, retention times
were exactly the same and the dierence in SRM ratios was
solely 6%, and thus, conrming the identication
The described methodology probed to be precise and
sensitive for the quantication of OCT in dolphin liver samples
aording method limits of detection (LOD) and quantication
(LOQ) of 23 and 75 ng g1lipid weight (lw), respectively, and
a relative standard deviation of 9%.
OCT Concentration in Liver Tissue. The analysis of the
samples revealed that OCT was present in 21 out of the 56
samples analyzed (38% frequency of detection) with concen-
trations in the range 89782 ng g1lw (see Table 1). These
concentrations are notoriously higher than that reported by
Balmer et al.
for OCT in lake sh (25 ng g1lw). This
outcome was expected, as with other organic pollutants that
bioaccumulate and biomagnify along the food chain, given the
higher trophic level occupied by dolphins.
From the six sampling areas selected, Rio de Janeiro was one
of the areas where we expected to nd residues of the sunscreen
because of its beach area with very active aquatic activities.
However, in the only sample taken OCT was not detected.
Despite that, we cannot rule out its presence in the area since
Table 1. continued
location Brazilian State sample code sex length sexual maturity physical maturity sampling date (year) concentration OCT (ng g1lw)
CA 255 M 106 Im Ju 2001 nd
In parentheses, the number of samples analyzed, nd: not detected, uk: unknown, na: not available, FT: percentage of positive samples within the
area, Ca: Calves, Im: immature, Ma: mature, Ju: juvenile, Ad: adult. Method limit of detection (MLOD) and method limit of quantication (MLOQ)
are 23 and 75 ng g1lw, respectively. Total frequency: 100 ×21/56 = 38%, Calves: 100 ×4/7 = 57%
Environmental Science & Technology Article |Environ. Sci. Technol. 2013, 47, 561956255622
we were only able to analyze one sample. In contrast, the most
contaminated zone was São Paulo, where OCT was most
frequently detected (70%), followed by Rio Grande do Sul,
where the UV lter was observed in 8 out of the 19 dolphins
sampled, and at the highest concentration, 782 ng g1lw.
Nevertheless, the geographical distribution of positive samples,
as depicted in Figure 3, indicated that the highest mean
concentration (373 ng g1lw) was determined in the samples
from Santa Catarina State. This sampling area is a partially
enclosed estuarine receiving industrial and urban wastewater
discharge, which could act as a sink for anthropogenic
pollutants. In a recent study with polybrominated diphenyl
ethers (PBDEs) in the same samples from this work, it was
observed also the higher levels in the dolphins from this
disturbed bay, in Santa Catarina.
Similar mean concentrations
were reported for OCT and for the group of PBDEs. The
comparison of the concentrations observed in the rest of areas
evidenced a dierent source for OCT and PBDEs anthro-
pogenic emissions. The geographical distribution of mean
concentrations (ng g1lw) for OCT was: 373 (SC) > 310 (ES)
> 298 (RS) > 241 (SP) >129 (PR), whereas for the group of
congeners of PBDEs it was: 432 (SC) > 329 (SP) > 156 (PR)
> 144 (ES) >37 (RJ) > 34 (RS).
From 1994 to 2009 there has been a steady growing use of
UV lters as society has become aware of the dangerous eects
of sunlight. These currently popular chemicals have shown to
have a protective role against photoaging, photocarcinogenesis
and photoimmunosuppression promoted by UV sun radia-
Thus, potential temporal changes in the bioaccumu-
lation behavior of OCT were also assessed taking into account
the increasing use of sunscreen products. However, a direct
correlation could not be identied.
Relationships Between OCT Concentration and Bio-
logical Characteristics. The inclusion of individuals with
varying biological characteristics in this study provided an
opportunity to examine contaminant liver tissue concentrations
in relation to lipid content, sex, and physical and sexual
The trend of increased concentration in biota samples with
increasing lipid content may be observed for a number of
organic pollutants.
In an attempt to assess the behavior of the
lipophilic UV lter, the correlation between liver lipid content
and OCT concentration was evaluated, however, no correlation
could be established based on these parameters (linear least-
squares regression coecient of 0.371). The reason for this
dierential behavior remains unclear.
Many studies have reported gender-specicdierences in the
concentrations of persistent organic pollutants in marine
mammals, showing the well-known high variation in the
burden of lipophilic pollutants of females due to reproductive
Therefore, the potential correlation between sex and
OCT concentration was also assessed. Dierent statistical tests
were carried out, Pearson, Kendall, and Spearman. All they
showed no statistical dierences among OCT concentrations
and gender. Signicance values were: Pearson, 0.225; Kendall,
0.397; Spearman, 0.411.
Nevertheless, potential maternal transfer cannot be ruled out.
In order to assess the mother-to-calf transfer of OCT, a sample
of placenta from one pregnant female dolphin was collected
and analyzed, revealing that OCT was present in both the
placenta and the liver tissue at concentrations below LOQ (61
ng g1Lw semiquantitative analysis) and 130 ng g1lw,
respectively (liver sample reference BP151 in Table 1) being
indicative of gestational transfer. This hypothesis, however,
cannot be fully conrmed without data on a higher sample size
of pregnant female dolphins. However, it must be taken into
account the great diculty in obtaining this kind of samples.
On the other hand, contamination data on breast milk could
also support the maternal transfer, specically lactation transfer,
of the bioaccumulated OCT. This fact recently has already been
characterized in humans. Reported levels of OCT in women
breast milk were in the range 4.70135 ng g1lw, with 67%
frequency of detection.
This transfer was consistent with the
OCT accumulation data obtained in the present study, where
OCT was found in four out of the seven analyzed calves (57%
frequency of detection) higher than the frequency estimated
considering the complete set of individuals (38%), and at
increasing concentrations (129524 ng g1lw) as their length
was greater. Nevertheless, it has to be highlighted that,
Figure 2. Reconstructed SRM reference chromatogram for OCT
corresponding to a standard solution at 40 ng mL1(a and b), and a
chromatogram corresponding to a dolphin liver sample from an adult
male (sample code BP 176) from Sao Paulo (c and d).
Figure 3. Distribution of OCT mean concentrations in dolphins liver
(ng g1Lw) and standard error, along the Brazilian coast sampling
Environmental Science & Technology Article |Environ. Sci. Technol. 2013, 47, 561956255623
obviously, the exposure pathways of human and dolphins are
clearly dierent.
Biomagnication. Several studies have probed that
biomagnication can occur for lipophilic organic contaminants.
In addition to high concentration levels, the process that
produce biomagnication also results in age (or length)-specic
patterns for adult male marine mammal. A dierent pattern has
been reported for adult female mammals despite being exposed
to contamination similarly to males. During gestation and
lactation contaminant body burden deceased by transfer to
In order to probe the potential biomagnication of OCT, a
full trophic analysis of this compound must be accomplished.
However, as lower trophic level organisms on these areas were
not available, we tried to provide preliminary evidence by
comparing our results with published data on the terrestrial
food chain. To date solely one study reported data on UV lter
biomagnications. Fent et al.
recently investigated the
accumulation in the terrestrial food chain of EHMC, an UV
lter, having a similar lipophilicity (log Kow 6.1) to that of
OCT. The dierences in EHMC concentrations in cormorant,
sh and macroinvertebrates suggested a trend for biomagni-
cation. Cormorants are migratory sh eating birds, representing
a high terrestrial trophic level. Average concentrations of
EHMC in ve of these birds was 341 ng g1lw, with values in
the range 16701 ng g1lw, whereas decreased average
concentrations were observed in lower trophic levels. This
concentration range was comparable to that obtained for OCT
in the present study (89782 ng g1lw). It must be pointed
out that cormorants are migratory birds with high metabolic
capacity and whose exposure routes in the terrestrial environ-
ment are dierent from that of the dolphins of the present
study, which are coastal and nonmigratory. Therefore, we
cannot perform an accurate comparison between these two
In summary, these ndings demonstrate for the rst time that
the extensively used sunscreen agent OCT accumulates in liver
of dolphins at high concentration levels (up to 782 ng g1lw)
similar to those of anthropogenic organic persistent pollutants.
This study also provides evidence that maternal transfer may
occurs trough placenta and likely also through breast milk.
The results presented herein suggest that OCT biomagnies
through the marine food web. In order to probe the
biomagnication of this UV lter a full trophic level analysis
of OCT will be further performed. The present study
establishes the baseline levels for OCT in dolphins from
Brazilian coastal waters. Eorts should be directed toward the
analysis of other marine organisms to assess the impact of OCT
as well as other extensively used UV lters and their
transformation products on marine ecosystems.
Corresponding Author
*Phone: +34 93 400 6100; fax +34 93 204 59 04; e-mail:
The authors declare no competing nancial interest.
This research was funded by the Spanish Ministry of Economy
and Competitiveness through the Project CEMAGUA
(CGL2007-64551/HID). This work was also partly supported
by the Generalitat de Catalunya (Consolidated Research
Group: Water and Soil Quality Group 2009-SGR-965). Gago-
Ferrero acknowledges his fellowship to Junta para la
Ampliación de Estudios (JAE). This research was also funded
by the Ministry of Education of Brazil e CAPES (fellowship to
M.B. Alonso Sandwich Programmee PDEE; Ciencias do
Mare Proc. 23038.051661/2009-18), Brazilian Research
Council e CNPq (Grant No. 304826/2008- 1), FAPERJ
(Jovem Cientista do Nosso Estado No. 101.449/2010), Mount
Sinai School of Medicine (NY/USA), Fogarty International
Center NIH/USA (grant 1D43TW0640). We are grateful to
the shermen and cetacean research group stas for the
assistance in eldwork, as well as Cetacean Society Interna-
tional (CSI), Society for Marine Mammalogy (SMM) and Yaqu
Pacha. A.F.A. and J.L.-B. have research grant from CNPq (PQ-
2) and FAPERJ (JCNE). We give special thanks to students
from Environmental Chemistry Lab (IDAEA-CSIC, Spain),
Radioisotope Lab (UFRJ e Brazil) and Aquatic Mammal and
Bioindicator Lab (UERJ e Brazil).
(1) Richardson, S. D. Environmental mass spectrometry: Emerging
contaminants and current issues. Anal. Chem. 2010,82, 47424774.
determination of nine organic UV-absorbing compounds (UV filters)
in environmental samples. J. Chromatogr., A 2008,1202,6474.
(3) Fent, K.; Zenker, A.; Rapp, M. Widespread occurrence of
estrogenic UV filters in aquatic ecosystems in Switzerland. Environ.
Pollut. 2010,158, 18171824.
(4) Gago-Ferrero, P.; Díaz-Cruz, M. S.; Barceló, D. Occurrence of
multiclass UV filters in treated sewage sludge from wastewater
treatment plants. Chemosphere 2011a,84 (8), 795806.
(5) Gago-Ferrero, P.; Díaz-Cruz, M. S.; Barceló, D. Fast pressurized
liquid extraction with in-cell purification and analysis by liquid
chromatography-tandem mass spectrometry for the determination of
UV filters and their degradation products in sediments. Anal. Bioanal.
Chem. 2011b,400, 21952204.
(6) Gago-Ferrero, P.; Díaz-Cruz, M. S.; Barceló, D. An overview of
UV-absorbing compounds (organic UV filters) in aquatic biota. Anal.
Bioanal. Chem. 2012,404, 25972610.
(7) Balmer, M. E.; Buser, H. R.; Muller, M. D.; Poiger, P. Occurrence
of some organic UV filters in wastewater, in surface waters, and in fish
from Swiss lakes. Environ. Sci. Technol. 2005,39 (2), 953962.
(8) Buser, H. R.; Balmer, M. E.; Schmid, P.; Kohler, M. Occurrence
of UV filters 4-methylbenzylidene camphor and octocrylene in fish
from various Swiss rivers with inputs from wastewater treatment
plants. Environ. Sci. Technol. 2006,40 (5), 14271431.
(9) Fent, K.; Kunz, P.; Gomez, E. UV filters in the aquatic
environment induce hormonal effects and affect fertility and
reproduction in fish. Chimia 2008,62,18.
(10) Brausch, J. M.; Rand, G. M. A review of personal care products
in the aquatic environment: Environmental concentrations and
toxicity. Chemosphere 2011,82, 15181532.
(11) Langford, K. H.; Thomas, K. V. Imputs of chemicals from
recreational activities into the Norwegian coastal zone. J. Environ.
Monit. 2008,10, 894898.
(12) Tarazona, I.; Chisvert, A.; León, Z.; Salvador, A. Determination
of hydroxylated benzophenone UV filters in sea water samples by
dispersive liquid-liquid microextraction followed by gas chromatog-
raphy-mass spectrometry. J. Chromatogr., A 2010,1217, 47714778.
(13) Danovaro, R.; Bongiorni, L.; Corinaldese, C.; Giovannelli, D.;
Damiani, E.; Astofi, P.; Greci, L.; Pusceddu, A. Sunscreens cause coral
bleaching by promoting viral infections. Environ. Health Perspect. 2008,
116, 441447.
(14) Nakata, H.; Murata, S.; Filatreau, S. Occurence and
concentrations of benzotriazole UV stabilizers in marine organisms
Environmental Science & Technology Article |Environ. Sci. Technol. 2013, 47, 561956255624
and sediments from the Ariake Sea, Japan. Environ. Sci. Technol. 2009,
15, 43 (18), 6920-6926.
(15) Gaspar, L. R.; Campos, Maia PMBG. Evaluation of the
photostability of different UV filter combinations in sunscreens. Int. J.
Pharm. 2006,307, 123128.
(16) Tanabe, S. Contamination and toxic effects of persistent
endocrine disrupters in marine mammals and birds. Mar. Pollut. Bull.
(17) Secchi, E. Review on the threats and conservation status of
Franciscana, Pontoporia blainvillei (Cetacea, Pontoporiidae). In
Biology, Evolution and Conservation of River Dolphins Within South
America and Asia, Wildlife Protection, Destruction and Extinction
Series; Ruiz-Garcia, M., Shostell, J., Eds.; Nova Publishers: New York,
(18) Reeves, R. R.; Smith, B. D.; Crespo, E. A.; Nortabartolo, G. D.
Dolphins, Whales and Porpoises: 20042010 Conservation Action Plan
for the Worlds Cetaceans; Gland, Switzerland and Cambridge, 2008.
(19) Ott, P. H. S.; E., R.; Moreno, I. B.; Danilewicz, D.; Crespo, E. A.;
Bordino, P.; Ramos, R.; Di Beneditto, A. P.; Bertozzi, C. P.; Bastida,
R.; Zanelatto, R.; Perez, J. E.; Kinas, P. G. Report of the working group
on fishery interactions. Latin Am. J. Aquat. Mammals 2002,1,5564.
(20) Alonso, M. B.; Eljarrat, E.; Gorga, M.; Secchi, E. R.; Bassoi, M.;
Barbosa, L.; Bertozzi, C. P.; Marigo, J.; Cremer, M.; Domit, C.;
Azevedo, A. F.; Dorneles, P. R.; Torres, J. P. M.; Lailson-Brito, J.;
Malm, O.; Barceló, D. Natural and anthropogenically-produced
brominated compounds in endemic dolphins from Western South
Atlantic: Another risk to a vulnerable species. Environ. Pollut. 2012a,
170, 152160.
(21) Alonso, M. B.; Feo, M. L.; Corcellas, C.; Vidal, L. G.; Bertozzi,
C. P.; Marigo, J.; Secchi, E. R.; Bassoi, M.; Azevedo, A. F.; Dorneles, P.
R.; Torres, J. P. M.; Lailson-Brito, J.; Malm, O.; Eljarrat, E.; Barceló,D.
Pyrethroids: A new threat to marine mammals? Environ. Int. 2012b,
(22) Secchi E. R.; Wang J. Y. Pontoporia blainvillei (Rio Grande do
Sul/Uruguay Subpopulation), IUCN Red List of Threatened Species;
International Union for Conservation of Nature: Gland, Switzer-
(23) Bícego, M. C.; Taniguchi, S.; Yogui, G. T.; Montone, R. C.;
Silva, D. A. M.; Lourenço, R. A.; Martins, C. S. D. C.; Sasaki, S. T.;
Pellizari, V. H.; Weber, R. R. Assessment of contamination by
polychlorinated biphenyls and aliphatic and aromatic hydrocarbons in
sediments of the Santos and Sao Vicente Estuary System, Sao Paulo,
Brazil. Mar. Pollut. Bull. 2006,52, 18041816.
(24) Dorneles, P. R.; Lailson-Brito, J.; Dirtu, A. C.; Weijs, L.;
Azevedo, A. F.; Torres, J. P. M.; Malm, O.; Neels, H.; Blust, R.; Das,
K.; Covaci, A. Anthropogenic and naturally-produced organobromi-
nated compounds in marine mammals from Brazil. Environ. Int. 2010,
(25) Lamparelli, M. L.; Costa, M. P.; Prósperi, V. A.; Bevilácqua, J. E.;
Araújo, R. P. A.; Eysink, G. G. L.; Pompeia, S. Sistema Estuarino de
Santos e São Vicente; CETESB: Relatório Técnico. São Paulo, 2001.
(26) European Commission. Commission Decision, 2002/657/EC of
12 August, O. J. European Communities, Belgium, L221/ 8, 2002.
(27) Whitmore, S. E.; Morison, W. L. Prevention of UVB-induced
immunosuppression in humans by a high sun protection factor
sunscreen. Arch. Dermatol. 1995,131, 112833.
(28) Seite, S.; Colige, A.; Piquemal-Vivenot, P. A. full-UV spectrum
absorbing daily use cream protects human skin against biological
changes occurring in photoaging. Photodermatol. Photoimmunol.
Photomed. 2000,16, 14755.
(29) Liardet, S.; Scaletta, C.; Panizzon, R. Protection against
pyrimidine dimers, p 53, and 8-hydroxy-2-deoxyguanosine expression
in ultraviolet-irradiated human skin by sunscreens: Difference between
UVB + UVA and UVB alone sunscreens. J. Invest. Dermatol. 2001,117,
(30) Coat, S.; Monti, D.; Legendre, P.; Bouchon, C.; Massat, F.;
Lepoint, G. Organoclorine pollution in tropical rivers (Guadeloupe):
Role of ecological factors in food web bioaccumulation. Environ. Pollut.
2011,159, 16921701.
(31) Weijs, L.; Dirtu, A. C.; Das, K.; Gheorghe, A.; Reijnders, P. J. H.;
Neels,H.;Blust,R.;Covaci,A.Inter-species differences for
polychlorinated biphenyls and polybrominateddiphenyl ethers in
marine top predators from the Southern North Sea. Part 2.
Biomagnification in harbor seals and harbor porpoises. Environ. Pollut.
2009,157, 44545.
(32) Schlumpf, M.; Kypke, K.; Wittassek, M.; Angerer, J.; Mascher,
D.; Vökt, C.; Birchler, M.; Lichtensteiger, W. Exposure patterns of UV
filters, fragances, parabens, phthalates, organochlor pesticides, PBDEs,
and PCBs in human milk: Correlation of UV filters with use of
cosmetics. Chemosphere 2010,81 (10), 11711183.
(33) Wolkers, H.; Hammill, M. O.; van Bavel, B. Tissue-specific
accumulation and lactational transfer of polychlorinatedbiphenyls,
chlorinated pesticides, and brominated flame retardants in hooded
seals (Cistophora cristata) from the Gulf of St. Lawrence: Application
for monitoring. Environ. Pollut. 2006,142, 476486.
Environmental Science & Technology Article |Environ. Sci. Technol. 2013, 47, 561956255625
... Specifically, the Baixada Santista Metropolitan Region (BSMR) has a historical emission of contaminants to the marine environment (Martins et al., 2011;Buruaem et al., 2013;Roveri et al., 2021;Cassita and David, 2022). Consequently, previous studies point out the exposure to chemicals and associated deleterious effects on estuarine and marine invertebrates (Campolim et al., 2018;Bordon et al., 2020;Cassita and David, 2022) and vertebrates such as teleosts (Azevedo et al., 2009Magalhães et al., 2017;De Albergaria-Barbosa et al., 2018), sharks and batoids (Cascaes et al., 2014;Martins et al., 2021a), and mammals (Yogui et al., 2011;Gago-Ferrero et al., 2013;Alonso et al., 2015). ...
... The concentrations reported for octocrylene in elasmobranchs were unexpected (<LOQ -8.03 ng g −1 w.w.; median 0.01 ng g −1 w.w), due to the higher concentrations reported for cetaceans in southeastern Brazil (Alonso et al., 2015;Gago-Ferrero et al., 2013). Furthermore, Martins et al. (2020) also observed higher concentrations in P. horkelii in southern Brazil, yet guitarfish were sampled in austral summer months. ...
The present study aimed to determine persistent organic pollutants (POPs) and contaminants of emerging concern in endangered angelshark and guitarfish species from southeastern Brazil, and to investigate potential impacts of these compounds on morphometric indexes. Pesticides of emerging concern, pharmaceutical and personal care products (PPCPs), polycyclic aromatic hydrocarbons (PAHs), and polybrominated diphenyl ethers (PBDEs) were determined in hepatic and muscular tissues of Pseudobatos horkelii, P. percellens, Squatina guggenheim, and Zapteryx brevirostris obtained from artisanal and industrial fisheries operating in southeastern Brazil. Accumulation profiles and effects of contaminants on condition factor and hepatosomatic index were investigated. No differences were detected regarding species contaminant concentration, potentially due to similarities in habits, occurrence and trophic position shared by guitarfishes and angelsharks. Polycyclic aromatic hydrocarbons (23.2-495.3 ng g -1), and PPCPs such as diclofenac (<LOQ - 448.4 ng g-1) and methylparaben (<LOQ - 645.5 ng g-1) presented the highest concentrations, regardless of the species. Effects of elasmobranch size were not significant on contaminant levels, indicating the lack of bioaccumulation over time. We suggest that the exposure to contaminants in elasmobranchs inhabiting this region is highly dependent on the economic activities and high urban development in southeastern Brazil. Regarding potential impacts of such exposure, the condition factor was only negatively influenced by PBDEs concentrations, whereas the hepatosomatic index was not influenced by any contaminant. Despite this, our results indicate that guitarfishes and angelsharks are exposed to POPs and contaminants of emerging concern potentially toxic to aquatic organisms. In this context, more refined biomarkers should be used to predict potential impacts of these contaminants on elasmobranch's health.
... UV filters were reported in mussels (2-7112 ng g −1 d.w.) [32], crustaceans (< 10-68.9 ng g −1 d.w.) [33], various species of marine and freshwater fish (< LOD-680 ng g −1 d.w.) [34,35], and in sea mammals (89-782 ng g −1 l.w.) [36]. Fent et al. [37] monitored the widespread occurrence of UV filters at different trophic levels indicating the bioaccumulation of EHMC in the food chain. ...
... However, the toxic effect of UV filters on various organisms is not fully understood [69] and still requires some new clues and pieces of evidence. Additionally, ecotoxicological studies on organic UV filters most often prioritize an assessment of toxicity on organisms from higher trophic levels such as fish [34,35,37,61,70], mammals [36], and birds [37,71]. ...
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UV filters in environmental compartments are a source of concern related to their ecotoxicological effects. However, little is known about UV filters’ toxicity, particularly those released into the environment as mixtures. Acute toxicity of nine organic UV filters benzophenone-1, benzophenone-2, benzophenone-3, 4-methoxy benzylidene camphor, octocrylene, ethylhexyl methoxycinnamate, 2-ethylhexyl salicylate, homosalate, and butyl methoxydibenzoylmethane was determined. UV filter solutions were tested as single, binary, and ternary mixtures of various compositions. Single solutions were tested using a set of bio tests, including tests on saline crustaceans ( Artemia franciscana ), freshwater crustaceans ( Daphnia magna ), marine bacteria ( Aliivibrio fischeri ), and freshwater plants ( Lemna minor ). The tests represent different stages of the trophic chain, and hence their overall results could be used to risk assessment concerning various water reservoirs. The toxicity of binary and ternary mixtures was analyzed using the standardized Microtox ® method. Generally, organic UV filters were classified as acutely toxic. Octocrylene was the most toxic for Arthemia franciscana (LC 50 = 0.55 mg L –1 ) and Daphnia magna (EC 50 = 2.66–3.67 mg L –1 ). The most toxic against freshwater plants were homosalate (IC 50 = 1.46 mg L –1 ) and octocrylene (IC 50 = 1.95 mg L –1 ). Ethylhexyl methoxycinnamate (EC 50 = 1.38–2.16 mg L –1 ) was the most toxic for marine bacteria. The least toxic for crustaceans and plants were benzophenone-1 (EC 50 = 6.15–46.78 mg L –1 ) and benzophenone-2 (EC 50 = 14.15–54.30 mg L –1 ), while 4-methoxy benzylidene camphor was the least toxic for marine bacteria (EC 50 = 12.97–15.44 mg L –1 ). Individual species differ in their sensitivity to the tested organic UV filters. An assessment of the toxicity of mixtures indicates high and acute toxicity to marine bacteria after exposition to a binary mixture of benzophenone-2 with octocrylene, 2-ethylhexyl salicylate, or homosalate. The toxicity of mixtures was lower than single solutions predicting antagonistic interaction between chemicals. Graphical abstract
... Vila et al. (2016) recorded high concentration of BP-3 in Spain (692 mg.L À1 ), during summer in tourist areas. Studies have reported concentrations of UV filters, including BP-3, in aquatic organisms, such as bivalves (Groz et al. 2014;He et al. 2019), crustaceans (He et al. 2017), eels (Fent et al. 2010), freshwater (Zenker et al. 2008) and marine fish (Molins-Delgado et al. 2018), marine mammals (Gago-Ferrero et al. 2013a), seabirds (Molins-Delgado et al. 2017), and aquatic plants (Aznar et al. 2017). Due to their lipophilic properties (Log Kow ¼ 3.79) and relative stability to biotic degradation, UV filters tend to accumulate in biological tissues, such as muscle and adipose tissue (Gago-Ferrero et al. 2013b;Vione et al. 2013). ...
Personal care products, such as UV filters, are frequently present in aquatic ecosystems, but studies on their impact on marine organisms are still scarce. Here we addressed the effects of benzophenone-3 (BP-3) on the antioxidant status of Perna perna mussels exposed to concentrations of 0.1 and 3 μg.L-1 for 72 h and 7 days. Glutathione peroxidase (GPx), glutathione reductase (GR), glutathione S-transferase (GST), glucose-6-phosphate dehydrogenase (G6PDH) activity and lipoperoxidation (MDA) were evaluated in the gills. A significant reduction (p < 0.05) in the activity of G6PDH and GPx was observed after exposure for 7 days to 0.1 µg.L-1. However, no significant differences were observed in GST activity and MDA levels, independently of the exposure time. Principal component analysis (PCA) showed an association of BP-3 highest concentration with GR and MDA at 72 h and only with GR at 7 days of exposure. Similarly, the integrated biomarker response (IBR) demonstrated GR and MDA alterations. In conclusion, environmentally relevant concentrations of BP-3 altered antioxidant and auxiliary enzymes, which could cause long-term damage to P.perna mussels. The need to implement more efficient techniques in wastewater treatment systems is pointed out, especially in summer, when UV filters are used more frequently and abundantly.
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Este livro apresenta a toninha, a espécie de golfinho mais ameaçada de extinção do Atlântico Sul. Inclui uma revisão dos conhecimentos sobre a espécie, e uma recomendação de caminhos a seguir que podem retirar a toninha do caminho da extinção. Em síntese, este documento trata de uma revisão bibliográfica atualizada sobre o estado atual de conhecimentos sobre a toninha, um pequeno golfinho sob forte ameaça de extinção, e que ocorre apenas em três países da América do Sul: o Brasil, o Uruguai e a Argentina. A meta dos autores é que este material, produzido em língua portuguesa e de livre acesso, tenha um alcance maior e mais efetivo a membros da sociedade não acadêmica sul-americana, quando comparado à considerável carga de documentos científicos produzidos até aqui, em parte listada ao final deste documento, e que está inacessível a quem não é cientista; ou pelo fato dessa literatura ser quase que exclusivamente escrita em língua inglesa, ou por estar disponível apenas em meios que somente os cientistas foram capacitados e autorizados a procurar e a acessar. Escrito em uma linguagem mais compreensível a não acadêmicos, mas mantendo a estrutura de apresentação corriqueira de trabalhos escritos por cientistas para familiarizar a comunidade não cientista a essa estrutura textual, poderá alcançar uma maior audiência; preferencialmente aqueles atores da sociedade que não podem ser deixados de lado no árduo desafio de lutar pela conservação deste indefeso golfinho.
The benzotriazole UV stabilizer UV-328 is well known for its potent antioxidative properties; however, there are concerns about how it may affect signaling nodes and lead to negative consequences. This study identified the key signaling cascades involved in oxidative stress in zebrafish (Danio rerio) larvae and evaluated the cell cycle arrests and associated developmental alternations. Exposure to UV-328 at 0.25, 0.50, 1.00, 2.00, and 4.00 μg/L downregulated gene expression associated with oxidative stress (cat, gpx, gst, and sod) and apoptosis (caspase-3, caspase-6, caspase-8, and caspase-9) at 3 days postfertilization (dpf). The transcriptome aberration in zebrafish with disrupted p38 mitogen-activated protein kinase (MAPK) cascades was validated based on decreased mRNA expressions of p38 MAPK (0.36-fold), p53 (0.33-fold), and growth arrest and DNA damage-inducible protein 45 α (Gadd45a) (0.52-fold) after a 3- and 14-day exposure alongside a correspondingly decreased protein expression. The percentage of cells in the Gap 1 (G1) phase increased from 69.60% to a maximum of 77.07% (p < 0.05) in the 3 dpf embryos. UV-328 inhibited the p38 MAPK/p53/Gadd45a regulatory circuit but promoted G1 phase cell cycle arrest, abnormally accelerating the embryo hatching and heart rate. This study provided mechanistic insights that enrich the risk profiles of UV-328.
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The presence of ultraviolet filters (UVFs) and stabilizers (UVSs) was evaluated for the first time in the common bottlenose dolphin (Tursiops truncatus). UVFs and UVSs are compounds of growing concern because their effects on the environment are not completely known. UVFs and UVSs are added to personal care products (PCPs), such as cosmetics and products related to sun care and once released to the aquatic ecosystem, marine organisms can bioaccumulate these substances. This work aimed to determine the presence of 12 UVFs and UVSs in cetacean blubber samples to assess the pollution to which these animals of the highest trophic chain levels are exposed due to human activity. Analytical determinations were carried out using a method based on microwave-assisted extraction combined with ultrahigh-performance liquid chromatography and tandem mass spectrometry detection. The developed method was successfully applied to determine the target compounds in the blubber tissues of five necropsied common bottlenose dolphins. Three of the 12 studied compounds, namely 2-ethylhexyl 2-cyano-3,3-diphenylprop-2-enoate (octocrilene, OC), 2-hydroxy-4-methoxybenzophenone (benzophenone 3, BP3) and 3-methylbutyl (E)-3-(4methoxyphenyl) prop-2-enoate (IMC), were detected in several samples. Of the identified compounds, OC was present in all the samples and at the highest concentration within the range from 52.61 ± 18.59 to 108.0 ± 11.32 ng·g-1.
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Marine organisms have gained considerable biotechnological interest in recent years due to their wide variety of bioactive compounds with potential applications. Mycosporine-like amino acids (MAAs) are UV-absorbing secondary metabolites with antioxidant and photoprotective capacity, mainly found in organisms living under stress conditions (e.g., cyanobacteria, red algae, or lichens). In this work, five MAAs were isolated from two red macroalgae (Pyropia columbina and Gelidium corneum) and one marine lichen (Lichina pygmaea) by high-performance countercurrent chromatography (HPCCC). The selected biphasic solvent system consisted of ethanol, acetonitrile, saturated ammonium sulphate solution, and water (1:1:0.5:1; v:v:v:v). The HPCCC process for P. columbina and G. corneum consisted of eight separation cycles (1 g and 200 mg of extract per cycle, respectively), whereas three cycles were performed for of L. pygmaea (1.2 g extract per cycle). The separation process resulted in fractions enriched with palythine (2.3 mg), asterina-330 (3.3 mg), shinorine (14.8 mg), porphyra-334 (203.5 mg) and mycosporine-serinol (46.6 mg), which were subsequently desalted by using precipitation with methanol and permeation on a Sephadex G-10 column. Target molecules were identified by HPLC, MS, and NMR.
Diethylamino hydroxybenzoyl hexyl benzoate (DHHB), an ultraviolet (UV) filter, can be found in sunscreens and other personal care products and thus can be introduced into swimming pools through the swimmers. In outdoor pools, DHHB will inevitably interact with free chlorine and sunlight. Therefore, the mechanism of solar‑chlorine chemical transformation of DHHB, as well as the environmental risk, were investigated in this work. In chlorinated with solar (Cl + solar) process, free chlorine was the dominant contributor to 85 % of the DHHB degradation, while hydroxyl radicals and reactive chlorine species contributed only 15 % because of low free radical generation and fast DHHB and free chlorine reaction rates. Scavenging matrices, such as Cl-, NH4+, and dissolved organic matter (DOM), inhibited the degradation of DHHB in the Cl + solar process, while Br-, HCO3-, NO3-, and urea promoted DHHB degradation. DHHB degradation was inhibited in tap water swimming pool samples, while it was enhanced in seawater pool samples by the Cl + solar process. Seven transformation by-products (TBPs) including mono-, dichlorinated, dealkylate, and monochloro-hydroxylated TBPs were identified. Three degradation pathways, chlorine substitution, chlorine and hydroxyl substitution, and dealkylation were proposed for DHHB transformation in the Cl + solar process. Both Quantitative structure-activity relationship and Aliivibrio fischeri toxicity tests demonstrated increased toxicity for the chlorinated TBPs. A risk assessment of the DHHB and its TBPs suggested that both DHHB and its chlorinated TBPs pose a significant health risk.
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Franciscana's restriction to shallow coastal waters makes it highly vulnerable to anthropogenic threats. Habitat degradation (noise pollution, chemical pollution and overfishing) and loss affect many coastal cetacean species around the world. Nonetheless, incidental catches in fishing gear are believed to be the main threat to franciscana conservation. This chapter aims at providing a review about the main conservation issues for franciscana with emphasis on bycatch in fishing gear. It also discusses the species conservation status, the potential alternatives for minimizing incidental mortality in fisheries and the constraints for the effective establishment and implementation of conservation measures.
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UV-absorbing organic chemicals (UV filters) are being increasingly used in sunscreens, personal care products and in the protection of materials against UV irradiation. Environmental contamination originates from direct input from recreational activities and wastewaters. Concentrations in treated wastewaters are in the lower ?g/l range, whereas in rivers and lakes they are in the range of a few up to hundreds of ng/l. It is known that lipophilic UV filters accumulate in aquatic biota, but only little is known about their environmental fate. A large number of UV filters elicit hormonal effects in vitro. Estrogenic activity has also been demonstrated for some UV filters in fish in vivo. Benzophenone-1 (BP1), benzophenone-2 (BP2), 3-benzylidene camphor (3BC) and ethyl-4-aminobenzoate (Et-PABA) lead to induction of vitellogenin. 3BC and BP2 cause feminization in secondary sex characteristics of male fish, alteration of gonads in male and female fish and decrease in fertility and reproduction. The lowest observed effect concentrations for 3BC and BP2 were 3 ?g/l and 1.2 mg/l, respectively. UV filter mixtures show mainly a synergistic activity in vitro, whether this is also reflected by the in vivo activity is under investigation. In conclusion, a hazard and risk for aquatic ecosystems cannot be ruled out for the UV filter 3BC, where histological and reproductive effects occurred in fish at low concentrations. However for BP1, BP2 and Et-PABA an environmental risk is rather low based on current knowledge.
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The purpose of this article is to summarize biological monitoring information on UV-absorbing compounds, commonly referred as organic UV filters or sunscreen agents, in aquatic ecosystems. To date a limited range of species (macroinvertebrates, fish, and birds), habitats (lakes, rivers, and sea), and compounds (benzophenones and camphors) have been investigated. As a consequence there is not enough data enabling reliable understanding of the global distribution and effect of UV filters on ecosystems. Both liquid chromatography and gas chromatography coupled with mass spectrometry-based methods have been developed and applied to the trace analysis of these pollutants in biota, enabling the required selectivity and sensitivity. As expected, the most lipophilic compounds occur most frequently with concentrations up to 7112 ng g(-1) lipids in mussels and 3100 ng g(-1) lipids (homosalate) in fish. High concentrations have also been reported for 4-methylbenzilidenecamphor (up to 1800 ng g(-1) lipids) and octocrylene (2400 ng g(-1) lipids). Many fewer studies have evaluated the potential bioaccumulation and biomagnification of these compounds in both fresh and marine water and terrestrial food webs. Estimated biomagnification factors suggest biomagnification in predator-prey pairs, for example bird-fish and fish-invertebrates. Ecotoxicological data and preliminary environmental assessment of the risk of UV filters are also included and discussed.
Background and Design: To date, studies of the effectiveness of sunscreens in preventing UVB-induced suppression of contact hypersensitivity in humans have not been published. Several studies in mice of the protection afforded by sunscreens from UVB-induced suppression of contact hypersensitivity and rejection of transplanted skin cancers have yielded dissimilar results, ranging from ''no'' to ''complete'' protection. We sought to determine whether the effect of preapplication of a sun protection factor (SPF) 29 sunscreen (containing octyl methoxycinnamate, oxybenzone, and octyl salicylate) could prevent local UVB-induced suppression of contact hypersensitivity to dinitrochlorobenzene (DNCB). Nineteen subjects received either three minimal erythema doses of UVB daily on three consecutive days (UVB group) or sunscreen followed by this same dose of UVB irradiation (sunscreen plus UVB group) to a 16-cm2 area of the buttock. One day after completion of irradiation, DNCB was applied to this buttock site, and 2 weeks later, forearm challenge with four different concentrations of DNCB was performed. A control group of 10 subjects underwent DNCB testing as above, but with no prior exposure to UVB (no-UVB group). Results: The UVB group had a reduced response rate to all challenge doses of DNCB (3.125, 6.25, and 8.8 μg), except for the highest dose (12.5 μg) compared with the no-UVB control group (Fisher's Exact test, P≤.008), and compared with the sunscreen plus UVB group (P≤.02). The no-UVB and sunscreen plus UVB groups showed no significant differences in response rates to any of the doses of DNCB tested (P≥.53). Conclusions: These results indicate that application of a sunscreen with over ninefold greater protection than that needed to prevent erythema prior to localized UVB radiation prevents localized UVB-induced suppression of contact hypersensitivity. Further studies are needed to determine whether sunscreens providing less protection, yet still preventing erythema, adequately prevent suppression of contact hypersensitivity, a possible surrogate marker for skin cancer tumor antigen recognition and rejection.(Arch Dermatol. 1995;131:1128-1133)
A new sensitive method has been successfully developed and validated for the simultaneous determination and quantification of nine estrogenic UV filters (benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-4, 4,4-dihydroxybenzophenone, ethyl-4-aminobenzoate, 2-ethyl-hexyl-4-trimethoxycinnamate, 3-(4-methylbenzylidene)-camphor, 3-benzylidene-camphor) in different environmental matrices. After optimisation of extraction conditions for the best recovery of polar to lipophilic compounds from fish tissue and a subsequent lipid clean-up in HPLC, fish extraction recoveries exceeded 72% for all nine UV filters. Identification and quantification of compounds was performed for lipophilic UV filters with gas chromatography-electroionisation-mass spectrometry and for polar and mid-polar compounds with liquid chromatography coupled to electrospray ionisation mass spectrometry. Instrumental detection limits (IDL) varied between 5 and 260 pg injected and method detection limits (MDL) were in the low ng/g lipids range for all test compounds. The described analytical methods are shown to be useful to screen for estrogenic UV filters in environmental samples such as fish and polar organic chemical integrative samplers.