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Phthalates are ubiquitous contaminants and endocrine-disrupting chemicals that can become trapped in the cuticles of insects, including ants which were recognized as good bioindicators for such pollution. Because phthalates have been noted in developed countries and because they also have been found in the Arctic, a region isolated from direct anthropogenic influence, we hypothesized that they are widespread. So, we looked for their presence on the cuticle of ants gathered from isolated areas of the Amazonian rainforest and along an anthropogenic gradient of pollution (rainforest vs. road sides vs. cities in French Guiana). Phthalate pollution (mainly di(2-ethylhexyl) phthalate (DEHP)) was higher on ants gathered in cities and along road sides than on those collected in the pristine rainforest, indicating that it follows a human-mediated gradient of disturbance related to the use of plastics and many other products that contain phthalates in urban zones. Their presence varied with the ant species; the cuticle of Solenopsis saevissima traps higher amount of phthalates than that of compared species. However, the presence of phthalates in isolated areas of pristine rainforests suggests that they are associated both with atmospheric particles and in gaseous form and are transported over long distances by wind, resulting in a worldwide diffusion. These findings suggest that there is no such thing as a “pristine” zone.
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Phthalate pollution in an Amazonian rainforest
Alain Lenoir
&Raphaël Boulay
&Alain Dejean
&Axel Touchard
Virginie Cuvillier-Hot
Received: 7 March 2016 /Accepted: 23 June 2016
#Springer-Verlag Berlin Heidelberg 2016
Abstract Phthalates are ubiquitous contaminants and
endocrine-disrupting chemicals that can become trapped in
the cuticles of insects, including ants which were recognized
as good bioindicators for such pollution. Because phthalates
have been noted in developed countries and because they also
have been found in the Arctic, a region isolated from direct
anthropogenic influence, we hypothesized that they are wide-
spread. So, we looked for their presence on the cuticle of ants
gathered from isolated areas of the Amazonian rainforest and
along an anthropogenic gradient of pollution (rainforest vs.
road sides vs. cities in French Guiana). Phthalate pollution
(mainly di(2-ethylhexyl) phthalate (DEHP)) was higher on
ants gathered in cities and along road sides than on those
collected in the pristine rainforest, indicating that it follows a
human-mediated gradient of disturbance related to the use of
plastics and many other products that contain phthalates in
urban zones. Their presence varied with the ant species; the
cuticle of Solenopsis saevissima traps higher amount of
phthalates than that of compared species. However, the pres-
ence of phthalates in isolated areas of pristine rainforests sug-
gests that they are associated both with atmospheric particles
and in gaseous form and are transported over long distances
by wind, resulting in a worldwide diffusion. These findings
suggest that there is no such thing as a Bpristine^zone.
Keywords Phthalates .Pollution .Tropical rainforests .
Ants .DEHP
Of all of the pollutants found across the globe, phthalates
(mainly di(2-ethylhexyl) phthalate (DEHP)) are some of the
most widely distributed. Phthalate esters are used in many
industrially made products, such as cosmetics, pesticide car-
riers, insect repellents, vinyl, cables, tubing, films, paints, ad-
hesives, PVC, and inks. They are also used as plasticizers (i.e.,
to make plastics more flexible). Because phthalate esters do
not chemically bind to plastic polymers, they migrate to the
surface of the polymer matrix where they may more easily
leach into the air, water, or food. They have been detected in
the air (including in aerosols), water, soil, different sediments,
Editorial Responsible: Constantini Samara
Electronic supplementary material The online version of this article
(doi:10.1007/s11356-016-7141-z) contains supplementary material,
which is available to authorized users.
*Alain Lenoir
Raphaël Boulay
Alain Dejean
Axel Touchard
Virginie Cuvillier-Hot
IRBI, Institut de Recherche sur la Biologie de lInsecte, CNRS UMR
7261, Université de Tours, Faculté des Sciences, Parc de Grandmont,
37200 Tours, France
Ecolab, Université de Toulouse, CNRS, INPT, UPS,
Toulouse, France
CNRS, UMR EcoFoG, AgroParisTech, Cirad, INRA, Université des
Antilles, Université de Guyane, 97310 Kourou, France
CNRS; UMR 8198, Unité Évolution, Écologie et Paléontologie,
Université de Lille, Lille, France
Environ Sci Pollut Res
DOI 10.1007/s11356-016-7141-z
and animal tissue, including that of humans (Teil et al. 2006;
Alves et al. 2007; Babich and Osterhout 2010; Williams et al.
2010;Gaudinetal.2011; Salapasidou et al. 2011;Choietal.
2012; Huang et al. 2013).
Hundreds of scientific papers and many newspaper articles
have chronicled the effects of endocrine-disrupting chemicals
(EDCs, mainlyphthalates, and bisphenol A), which have been
associated with human pathologies (e.g., negative effects on
the male reproductive tract, breast and testicular cancers, dis-
ruption of the neuroendocrine system, allergies, and asthma)
(Saillenfait and Laudet-Hesbert 2005a,b; Desdoits-
Lethimonier et al. 2012; Manzetti et al. 2014). Moreover, we
know that the toxicity of certain pollutants is greater than
previously thought and frequently results in transgenerational
effects (e.g., in fish; Schwindt et al. 2014). Furthermore, the
impact can be exacerbated by interactions between contami-
nants or Bcocktail effects^(e.g., pesticide combinations on
bees) (Vidau et al. 2011;Gilletal.2012) or between contam-
inants and natural stressors, including malnutrition, osmotic
perturbations, and global warming (Rhind 2009; Holmstrup
et al. 2010).
Phthalate air pollution has both acute and chronic effects
ranging from minor upper respiratory irritations to chronic
respiratory and heart diseases, lung cancer, acute respiratory
infections in children, and chronic bronchitis in adults. In ad-
dition, short- and long-term exposure to phthalate pollution
has also been linked to premature mortality and reduced life
expectancy (Kampa and Castanas 2008) and transgenerational
effects through epigenetic mechanisms (Doyle et al. 2013;
Manikkam et al. 2013; Rissman and Adli 2014). Many reports
have indicated that the phthalates found in dust in houses are
associated with asthma and allergies in both children and
adults (Ait Bamai et al. 2014).
Phthalates have been found on insect cuticles such as those
of ants, crickets, and honey bees, something which has been
taken as evidence of their ubiquity (Cavill and Houghton
1974;Katheretal.2011; Lenoir et al. 2012); they can also
become trapped in the wax of honey bee combs (Gómez-
Ramos et al. 2016). DEHP and dibutyl phthalate (DBP) are
toxic at high doses for Folsomia candida springtails, causing
modifications in symmetry (Jensen et al. 2001; Kristensen
et al. 2004). Phthalates deposited in large quantities on
Lasius niger ant cuticle remained in dead, control individuals,
while they were adsorbed and metabolized in less than 5 days
and so returned to their basic level, in live individuals (Lenoir
et al. 2014). At doses corresponding to chronic exposure
levels, phthalates reduce ant queen fecundity and stimulate
an immune response in workers (Cuvillier-Hot et al. 2014).
Because phthalates are transported everywhere in the atmo-
sphere above developed countries (Choi et al. 2012;
Blanchard et al. 2013) and because they have been found in
theArctic(Xieetal.2007), a region isolated from direct an-
thropogenic influences, they appear to be widespread. To
verify this, we hypothesized that their presence in isolated
pristine Amazonian rainforests would provide strongevidence
that the planets atmosphere is thoroughly polluted by these
Ants are present everywhere, are found in almost every part
of the food web, and constitute the most abundant animal
taxon in tropical ecosystems (Longino et al. 2014; see also
Basset et al. 2015 for tropical insect diversity).
Consequently, ants represent important bioindicators based
on the degree to which they have been contaminated by pol-
lution. So, we compared the phthalate pollution levels of ants
from isolated pristine rainforest in French Guiana, far from
any human activity, with areas having increasing levels of
anthropogenic perturbation, including urban areas, where
plastics and many products containing phthalates (e.g., deter-
gents, building materials, and furniture) are in constant use.
However, because phthalates are rapidly degraded by micro-
bial activity and abiotic processes (i.e., hydrolysis, photocata-
lytic oxidation, and photolysis) (Staples et al. 1997;Zhouetal.
2005; Yuan et al. 2010; Huang et al. 2013; Manzetti et al.
2014), the levels recorded are likely much lower than those
associated with the original source of contamination. We also
aimed to identify the various phthalates present because, due
to concerns over their safety, the most frequently used (i.e.,
DBP, diisobutyl phthalate (DiBP), and DEHP) are progres-
sively replaced by heavier molecules, which have already
been found in soft plastics produced in Asia (Barušićet al.
2015; AL, personal observation).
Materials and methods
We collected ants from various sites in French Guiana in
November 2013 (Fig. 1). The CNRS Nouragues research sta-
tion (40° 05N, 52° 40W, 121 m asl) was an important
sampling location in our study because it is situated in an
isolated, uninhabited, and protected area 90 km from the
coast and can be reached only by helicopter (or by pirogue
then a 4-h hike). We collected ants near the station, where
human activity may have served as a source of pollution
(i.e., different materials have been used to construct shelters,
and plastic has been brought in as a result of the provision of
food and research materialssee Suppl. 1). We also collected
ants in the rainforest far from the station and on the summit
(397 m) of the inselberg near the station (see Suppl. 2).
Exposed to the elements, it harbors sparse vegetation. We also
sampled ants near the Petit-Saut hydroelectric dam (4° 59N,
53° 08W) as well as in the forest of Crique Plomb, including
the dirt road which crisscrosses the forest over 10 km from the
road leading to the dam from Route N° 1, and in other forested
areas along this road. We also collected ants in and near the
cities of Sinnamary (5° 22N; 52° 57W), Kourou (5° 09N;
52° 38W), and Cayenne (4° 56N; 52° 20W).
Environ Sci Pollut Res
Ants were captured with metal forceps and placed di-
rectly into glass vials containing hexane; they were never
in contact with plastics and were left in the vials until the
analyses were run. At that point, they were removed from
the vials, and the solvent evaporated. Then, the extract
was redissolved in 10 μLofhexanetowhich2μLof
hexane containing 400 ng of eicosane (C20) was added as
an internal standard (we verified that all the hexane used
was phthalate free). We injected 2 μL of each redissolved
extract into a Perkin-Meyer gas chromatograph-mass spec-
trometer (GC-MS) functioning at 70 eV and with a source
temperature of 230 °C. The GC-MS was equipped with a
ZB-5HT column (30-m L×0.25-mmID×0.252μmdf;
5 % phenyl95 % dimethylpolysiloxane). The following
temperature program was used: 2 min at 80 °C, increased
by 10 °C/min to reach 320 °C, and a 10-min hold at
320 °C (for a total of 36 min). An external mixture of
phthalates is generally used to quantify phthalate acid es-
ters (PAEs) (Teil et al. 2006). Eicosane is frequently used
as the standard in hydrocarbon analyses, so we utilized it
here to compare this study with previous ones (Lenoir
et al. 2012,2014; Cuvillier-Hot et al. 2014). We used ion
149, typical of phthalates, as the basis for our analyses of
the phthalate peaks (Cao 2008; Valton et al. 2014; Barušić
et al. 2015). This method is less sensitive but much more
effective in differentiating phthalates from other hydrocar-
bons, particularly DEHP from 5MeC25 (Lenoir et al. 2014).
We calculated the quantity of each compound relative to the
eicosane internal standard. The threshold for DEHP
quantification is 0.20 ng, so that, for small ants, we placed
five workers in the extract vial. We analyzed a total of
243 samples.
Since the species ranged in size, the results were normal-
ized and presented in terms of nanogram per milligram of dry
weight (DW), as in Lenoir et al. (2014).
Data are presented as means ± standard errors (SE), and
statistical analyses were conducted using ANOVAs and the
Newman-Keuls post hoc test for multiple comparisons (R
Results and discussion
The different phthalates recorded
Guianese ants were contaminated with the same phthalates as
their European and North African counterparts (Lenoir et al.
2012), notably DEHP, DBP, diisobutyl phthalate (DiBP), and
benzyl butyl phthalate (BBP). DEHP, ubiquitous and noted in
95 % of the samples (Table 1), was found in higher quantities
on Solenopsis (19.5 ng/mg DW vs. 0.9 for other ants) and
accounted for 97 and 61.5 % of the phthalates found on
Solenopsis saevissima workers and other ants, respectively.
DEHP is also the most prevalent phthalate in the atmosphere
in the Paris region (Teil et al. 2016).
We also found on Guianese ant cuticules two new
phthalates, di(2-ethylhexyl) terephthalate ((DEHTP) =
dioctylterephthalate (DOTP)) and diisononyl phthalate 35
Fig. 1 Main ant sampling
locations. Map created using
Google Earth. A transect was
established along the road
between the Petit-Saut Dam and
the city of Sinnamary. Other main
places are Nouragues field
station, Kourou, and Cayenne
Environ Sci Pollut Res
isomers (DINP), which are recently being used instead of
DEHP (Rastogi 1998; Abe et al. 2012). DEHTP can be pas-
sively transferred by simple contact between ants and frag-
ments of plastic childrens toys (A. Lenoir, unpublished re-
sults), explaining why it occurred on urban Guianese ants.
DINP was detected in 22.7 % of Solenopsis and 31.8 % of
other ants gathered around the Nouragues research station and
in the cities of Cayenne (at the harbor), Kourou, and
Sinnamary; it was also noted at the Petit-Saut field station
and along the road to the dam. When present, DINP only
represented 1 to 2 % of the phthalates. In the Nouragues re-
search station, it was recorded in the pieces of flagging tape
tied around trees to delimit parcels. DINP is found in toys,
childcare products, PVC, flagging tape, and many soft plastics
(Barušićet al. 2015). Its metabolites have been detected in
human urine across the globe (Saravanabhavan 2012), and
although it seems to be less toxic than the more common
phthalates (Babich and Osterhout 2010), it was placed on
Californias official list of carcinogens (Tomar et al. 2013).
The plastic tubing used to delimit parcels at the Nouragues
research station contains BBP and DEHP in small quantities,
likely explaining their presence on ants. However, these com-
pounds were also noted on ants gathered far from any human
activity, such as the top of the inselberg.
Anthropogenic gradient of pollution
Classically, phthalate pollution levels increased from the
rainforest to the cities regardless of the ant taxa tested, showing
a relationship with human activity (Fig. 2). An ANOVA using
Table 1 Different phthalates
found on ants in French Guiana
for Solenopsis and all other ant
species (mean ng/mg DW ± SE,
% of samples containing
phthalates, % quantities related to
the total amount of phthalates)
Phthalates (ng/mg DW) Other species Solenopsis
Mean SE % Samples % Total Mean SE % Samples % Total
DBP 0.1 0.0 45.5 6.4 0.1 0.1 13.4 0.6
DiBP 0.04 0.0 25.5 2.9 0.01 0 12.4 0.1
BBP 0.4 0.1 39.1 27.6 0 0 0 0
DEHP 0.9 0.2 94.5 61.5 19.5 3.6 93.8 97.4
DINP 0.02 0 31.8 1.5 0.4 0.1 22.7 1.9
DEHTP 0.001 0.0 0.9 0.1 0 0 0 0
Total 1.4 100 20.0 100
n= 110 97
Forest (149) Road (16) City (64)
Fig. 2 Mean phthalate levels
pooled from the cuticles of the
different ant genera. Comparison
between individuals gathered
from the rainforest, along the
roads, and in the cities (mean ng/
mg DW ± SE). Statistical
comparisons: ANOVA
(F= 24.31; df 2; p< 0.0001) and
Newman-Keuls post hoc test;
different letters indicate
significant differences at
Environ Sci Pollut Res
Forest (49) Road (33) City (11)
Fig. 3 Mean phthalate levels for
the different ant genera in the
different areas along the road
from the Petit-Saut dam tothecity
of Sinnamary (mean ng/mg
DW ± SE). Statistical
comparisons: ANOVA (F=45.3;
df =2;p< 0.0001) and Newman-
Keuls post hoc test; different
letters indicate significant
differences at p<0.001
Gigantiops (12)
Atta (20)
Paraponera (4)
Eciton (5)
Azteca (1)
Pachycondyla (6)
Cephalotes (1)
Odontomachus (21)
Pheidole (5)
Ectatomma (13)
Dolichoderus (4)
Camponotus (73)
Dorymyrmex (10)
Solenopsis (68)
Fig. 4 Overall mean phthalate
levels for the different ant genera
(mean ng/mg DW ± SE).
Statistical comparisons: ANOVA
(F=6.576;df =14;p< 0.0001)
Environ Sci Pollut Res
the full data set revealed that phthalate levels, which
ranged from 0 to 200 ng/mg DW, differed significantly
across ant genus (F=6.57,df =14,p<001),areas
(i.e., rainforests vs. roads vs. cities, F=32.03,df =2,p<001),
but not with altitude (F=1.47,df =1,p= 0.226). Overall,
phthalate levels were significantly higher in urban areas
(p< 0.001) and there was an increase, albeit non-significant,
from road sides to cities (p= 0.45; Fig. 2). The same trend was
noted for the data from ants sampled in the rainforest of Petit-
Saut, along the road leading to the dam, and in the city of
Sinnamary (ANOVA (F=45.3;df =2;p< 0.0001); here, all
of the differences between areas were significant (Fig. 3ac).
The cuticular phthalate levels observed for urban Guianese
ants are similar to those noted for the ant L. niger in Europe
(i.e., 2 ng/ant fresh weight, corresponding to 5 ng/mg DW)
(Lenoir et al. 2012). Yet, a perfect comparison would require
using the same species.
Phthalates were ubiquitous around the Nouragues research
station, as they were found in ants from the camp, the forest,
and the top of the inselberg.The levels were low, ranging from
0.5 (the top of the inselberg) to 2 ng/mg DW, and did not differ
significantly between sites (p=0.06,butnearsignificancefor
the top of the inselberg, p= 0.055), so that human activity in
and around the station is not likely responsible for the phthal-
ate pollution noted deep in the rainforest and on the top of the
Therefore, our hypothesis that phthalate pollution is glob-
ally ubiquitous is likely confirmed as, in addition to their pres-
ence in the Arctic (Xie et al. 2007), we found them in other
areas isolated from direct anthropogenic influence, including
parts of the Amazonian rainforest and the top of an inselberg.
These results strongly suggest that contaminants arrive from
the atmosphere both with air particles and in gaseous form
(see Blanchard et al. 2014; Cecinato et al. 2012; Gao and
Wen 2016;Teiletal.2016; Xie et al. 2005). For example, in
the Paris region, phthalate pollution ranges from 10 to
100 ng m
of total air and 80 % in the gaseous phase. It is
more concentrated in urban areas compared to forest sites (Teil
et al. 2016).
Variation in phthalate levels across ant genera
The levels of phthalate contamination varied between ant gen-
era (Fig. 4), a pattern likely due to differences in cuticle com-
position (Vienne et al. 1995). S. saevissima had the highest
levels but was not found at the Nouragues research station nor
the rainforest (see Dejean etal. 2015). Yet, it did occur at all of
the other sites, including along the dirt road of Crique Plomb
which crisscrosses the rainforest at Petit-Saut. Phthalate levels
noted on workers were low in the latter case and high in the
cities with values of up to 180 ng/mg DW. Consequently, with
its anthills interconnected by galleries forming huge colonies
extending along several kilometers (Martin et al. 2011; Lenoir
et al. 2016), S. saevissima appears to be a good bioindicator
for gauging phthalate pollution in human-disturbed areas.
In conclusion, it appears that phthalates are universal con-
taminants and are probably major constituents of generalized
anthropogenic pollution, which is a leading cause of human
health problems. They may also be playing a role in the mass
extinctions of the Anthropocene, which are affecting both ver-
tebrate and, albeit less visibly, invertebrates (Dirzo et al.
2014). Phthalates are the major pollutants disseminated
throughout the world in gaseous form and on atmosphere
particles (Teil et al. 2016). Our results show that they are
found in different levels on ant cuticle based on a gradient of
urbanization, so ants can be considered good bioindicators
due to their ubiquity and ease of sampling them. It is thus
imperative to continue to study the pollution of ant popula-
tions, most particularly in tropical rainforests.
Acknowledgments Financial support for this study was provided by a
CNRS/Centre dÉtudes de la Biodiversité Amazonienne (CEBA) project
entitled BPhthalate pollution in an Amazonian rainforest^(PPAR). We are
grateful to Chloé Fasilleau and Chloé Moyse (École Polytechnique,
Université de Tours, France) for the analysis of the data, to Jessica
Pearce-Duvet and Andrea Yockey-Dejean for proofreading the manu-
script, and to Jacques H. C. Delabie (Laboratório de Mirmecologia,
CRC, Ilhéus, Bahia, Brazil) for the identification of the ants. We would
like to thank the staff of the CNRS Nouragues research station and the
Laboratoire Environnement de Petit-Saut for furnishing logistical assis-
Compliance with ethical standards
Conflict of interest The authors declare that they have no competing
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... For example, the half-life of DEHP ranges from 390 to 1600 days due to photolysis and hydrolysis [54]. PAEs have even been detected in remote areas such as the Atlantic, the Arctic Ocean [55], and the Amazon rainforest due to atmospheric transport [56]. For example, the average PAE concentration in PM 2 . ...
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The increasing consumption of phthalates (PAEs), along with their high toxicity and high mobility, poses a threat to the environment. This study presents initial data on the contents of six priority PAEs in the water of lakes located on the eastern shore of Lake Baikal-Arangatui, Bormashevoe, Dukhovoe, Kotokel, and Shchuchye. The mean total concentrations of the six PAEs in lakes Arangatui and Bormashevoe (low anthropogenic load) were comparable to those in Kotokel (medium anthropogenic load, 17.34 µg/L) but were significantly higher (p < 0.05) than in Dukhovoe and Shchuchye (high anthropogenic load, 10.49 and 2.30 µg/L, respectively). DBP and DEHP were the main PAEs in all samples. The DEHP content in lakes Arangatui and Bormashevoe was quite high, and at some sampling sites it exceeded the MACs established by Russian, U.S. EPA, and WHO regulations. The assessment showed that there is no potential risk to humans associated with the presence of PAEs in drinking water. However, the levels of DEHP, DBP, and DnOP in the water pose a potential threat to sensitive aquatic organisms, as shown by the calculated risk quotients (RQs). It is assumed that the origin of the phthalates in the studied lakes is both anthropogenic and biogenic.
... The nature of pollutants is diverse: physical such as light or noise, or chemical such as plastic and trace metals. While physical pollutants are more or less spatially localized, chemical pollutants are more diffuse and found in all ecosystems, even in those that were once considered as pristine (Lenoir et al. 2016). Pollution is not evenly distributed throughout the world, and some locations are more contaminated than others. ...
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A recent study showed that, in the ant Temnothorax nylanderi, city colonies are more tolerant to cadmium than forest colonies. However, because of annual variation in biological factors (e.g. body size, anti-stress protein production or trace metal accumulation rate), trace metal tolerance may vary over the year. We aimed at testing whether tolerance to cadmium of colonies of T. nylanderi differs between two different seasons within the same year (winter and spring). We also assessed whether the better cadmium tolerance of city colonies was constant over these two different time points. We collected colonies at the end of their hibernation period (winter colonies) and several weeks after (spring colonies) from two different habitats (forest and city) to assess whether response to cadmium was consistent regardless of the environment. We exposed colonies to a cadmium or a control treatment for 61 days. We compared tolerance to cadmium between spring/winter and city/forest colonies by measuring several life history traits. We found that spring colonies tolerates cadmium better than winter colonies, and that city colonies have a higher tolerance to cadmium but only in spring. Although further studies with replicated pairs of city/forest habitats and different years will be necessary to confirm those results, our study suggests that tolerance to trace metals can fluctuate along the yearly cycle.
... In contrast, diisobutyl phthalate, dibutyl phthalate, and toluene are well known anthropogenic pollutants and their presence in a pristine environment is of concern. Phthalates are ubiquitous contaminants that are adsorbed onto the cuticles of insects, including ants from the rainforest, which have been proposed as good bioindicators for such type of pollution [34]. This bioaccumulation may explain the higher concentration of diisobutyl phthalate and dibutyl phthalate inside inhabited domatia seen in this study (Table 1). ...
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Black fungi of the order Chaetothyriales are grown by many tropical plant-mutualistic ants as small so-called “patches” in their nests, which are located inside hollow structures provided by the host plant (“domatia”). These fungi are introduced and fostered by the ants, indicating that they are important for the colony. As several species of Chaetothyriales tolerate, adsorb, and metabolize toxic volatiles, we investigated the composition of volatile organic compounds (VOCs) of selected domatia in the Azteca/Cecropia ant-plant mutualism. Concentrations of VOCs in ant-inhabited domatia, empty domatia, and background air were compared. In total, 211 compounds belonging to 19 chemical families were identified. Ant-inhabited domatia were dominated by ketones with 2-heptanone, a well-known ant alarm semiochemical, as the most abundant volatile. Empty domatia were characterized by relatively high concentrations of the monoterpenes d-limonene, p-cymene and b-phellandrene, as well as the heterocyclic sulphur-containing compound, benzothiazole. These compounds have biocidal properties and are primarily biosynthesized by plants as a defense mechanism. Interestingly, most of the latter compounds were present at lower concentrations in ant inhabited domatia than in non-colonized ones. We suggest that Chaetothyriales may play a role in reducing the VOCs, underlining that the mutualistic nature of these fungi as VOCs accumulation might be detrimental for the ants, especially the larvae.
... The presence of high concentrations of phthalates in water collected from mangroves of Guaratiba State Biological Reserve, which includes Sepetiba Bay of Rio de Janeiro in this study, was reported by other authors [39]. Phthalates are distributed worldwide, even in isolated, pristine Amazon headwaters and rainforests, indicating that the planet's atmosphere is thoroughly polluted by these compounds [40]. Phthalates can be biodegraded at varying rates; but, in anaerobic environments, such as mangroves, their degradation is slow so that accumulation occurs in areas with little oxygenation [41]. ...
This study aimed to investigate the accumulation of phthalates in the leaf epicuticular wax of Avicennia schaueriana and Rhizophora mangle. Leaves were collected from plants situated in three mangroves around Sepetiba Bay, Rio de Janeiro state, Brazil. Dibutyl phthalate (DBP) and di-n-octyl phthalate (DnOP) were detected in higher content in A. shaueriana leaf wax (44.26%) and in R. mangle leaves at 34.43%. A high incidence of plastic residue pollutants in leaf epicuticular wax of these two mangrove species most likely results from absorption from substrate, water or air.
Phthalates (PAEs) are known environmental endocrine disruptors that have been widely detected in several environments, and many studies have reported the immunotoxic effects of these compounds. Here, we reviewed relevant published studies, summarized the occurrence and major metabolic pathways of six typical PAEs (DMP, DEP, DBP, BBP, DEHP, and DOP) in water, soil, and the atmosphere, degradation and metabolic pathways under aerobic and anaerobic conditions, and explored the molecular mechanisms of the toxic effects of eleven PAEs (DEHP, DPP, DPrP, DHP, DEP, DBP, MBP, MBzP, BBP, DiP(DiNP), DMP) on the immune system of different organisms at the gene, protein, and cellular levels. A comprehensive understanding of the mechanisms by which PAEs affect immune system function through regulation of immune gene expression and enzymes, increased ROS, immune signaling pathways, specific and non-specific immunosuppression, and interference with the complement system. By summarizing the effects of these compounds on typical model organisms, this review provides insights into the mechanisms by which PAEs affect the immune system, thus supplementing human immune experiments. Finally, we discuss the future direction of PAEs immunotoxicity research, thus providing a framework for the analysis of other environmental pollutants, as well as a basis for PAEs management and safe use.
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The linearity of the plastics economy is wasteful and polluting. To encourage recycling and decrease diversion to landfill, new legislation within the EU and UK will tax single-use plastic products made with less than 30% recycled plastic. At present, quantitative determination of recycled content is elusive and existing methods are inconsistent. We present a fluorescence-based analytical technique to determine recycled content in plastic and (single use) packaging. Bathochromic shifts resulting from aggregation of the fluorescent brightener 4,4'-bis(2-benzoxazolyl) stilbene (BBS) in three commodity plastics [high-density polyethylene, polypropylene, and poly(ethylene terephthalate)] at loadings ≤0.5 wt % were used to systematically quantify simulated recycled contents as low as 10 wt %. Linear correlations were found between recycled content and three fluorescence-based properties: emission, lifetime, and resulting color. We demonstrate how this multi-branched verification system is completely independent of sample dimensions and processing conditions, has a negligible effect on polymer properties, and is inexpensive and highly compatible with existing recycling infrastructure.
Mass production and insatiable consumption are leading to enormous waste worldwide, contaminating the entire biosphere, losing biodiversity, and climate change. Craving for materialistic things and buying sprees for newer products indicate the dominant roles of human behavior in imminent ecological, social, and economic crises. However, existing global environmental governance has failed to address the current consumption patterns, particularly in rich countries. There is no inclusive developmental policy that integrates human behavior intervention to reduce unnecessary consumption, closed-loop material flow systems to keep waste out of the system, and economic strategies addressing ecological disaster from a social equity standpoint. The paper is based on a critical literature review of three concepts, relevance of behavioral economics in pro-environmental decision making, scope and limitations of circular economy as technological solutions, and conflicts of ecological economics with dominant neoclassical economics pitting ‘degrowth’ as an alternative. The paper proposes a theoretical concept of a novel economic model (minimalonomics) that aims to provide an institutional framework for a minimalist lifestyle without compromising wellbeing, prosperity, equity, and justice. The model focuses on minimizing consumption at the individual and societal levels, integrating theories and principles of ecological economics and behavioral economics, and efficient application of circular economy. Minimalonomics emphasizes creating a pro-environmental attitude in all levels of society (producers, consumers, and government) and translating the individual's perspective to collective and coordinated action for protecting the biosphere. Contrary to the standard economic approach, minimalonomics restores the value of localization and appropriates local social and cultural norms regarding consumption, waste reduction, and environmental protection; thus, the model is more inclusive. Minimalonomics is a novel concept; therefore, before application to governance and policies, it needs further research on creating theories, developing indicators, and testing them in the field.
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Plasticizers are the most used polymer additives world-wide. Nowadays, conventional plasticizers (e.g. phthalates) do not meet the requirements in terms of renewability, biodegradability and cytotoxicity that have become necessary, especially if they are compounded with biopolymers. In this study, novel bioplasticizers are synthesized from levulinic acid by a protecting group-free three-steps process. After FT-IR and NMR characterization of the synthesized molecules, their plasticization effect has been tested in poly(3-hydroxybutyrate) (PHB) as a model semicrystalline biopolyester characterized by a narrow processing window, slow re-crystallization and high brittleness, which limit its processability and diffusion. The proposed bioplasticizers show remarkable miscibility with PHB and low leaching. The bioplasticizers also show a remarkable plasticization effect in terms of glass transition and melting temperatures reduction (approx. 17°C and 8°C, respectively), which are comparable with the performance of the best commercially available green plasticizers. Furthermore, flexibility and crystallinity are positively affected, leading to an overall reduction of the typical brittleness of PHB. The observed effects result in an expansion of the temperature range in which PHB can be processed without thermal degradation. Moreover, the incorporation of the levulinic acid-based molecules does not significantly affect the typical biodegradability and biocompatibility of PHB, showing their promising features as bioplasticizers for both environmental and biomedical applications.
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One hundred and twenty-eight stream sediment samples were collected in the Misiones province of Argentina by the low-density geochemical mapping project of the China Geological Survey. The analyzed data were used to study the concentration, spatial distribution, local pollution level and potential ecological risk of eight heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) by factor analysis, geoaccumulation index (Igeo), enrichment factor (EF) and the Hakanson’s potential ecological risk index (Eir and RI) methods. Results showed that the background values (median) of those elements were 2.97 ppm, 0.13 ppm, 212.60 ppm, 322.53 ppm, 0.013 ppm, 64.42 ppm, 12.58 ppm, and 198.85 ppm, respectively. Except for Hg, the contents of other elements were higher than the abundance of continental crust. The spatial distribution of Cu and Zn in stream sediments were consistent, while that of other elements were different. The factor analysis results implied that Cd, Cr, Cu, Ni and Zn were mainly affected by geological background and inherited the characteristics of regional parent rocks. Furthermore, Pb was not only controlled by natural conditions but also related to human activities, while As and Hg represented the anthropogenic sources, and their concentrations were affected by human activities. The results of Igeo and EF told us that Cu was heavily polluted in stream sediments; Pb and Zn were largely mildly polluted; As, Cr, Cd, Ni and Hg were mostly nonpolluted. The ecological risks were ordered as As > Cu > Cd > Pb > Hg > Cr > Ni > Zn. In general, the potential ecological risk of heavy metals in the Misiones province was low, but As and Cu also have a high ecological risk at some sampling points, which should be considered.
The pollution of phthalate esters (PAEs) remains an important issue in the world. Current studies mainly focused on atmospheric PAEs in urban area with strong anthropogenic activities, but there were no studies on PAEs in the ambient air around large natural lake. This paper focused on two sites around take Chaohu to investigate the monthly occurrence, composition and source of PAEs in the atmospheric particles around large shallow natural lake. New insights into atmospheric PAEs in large shallow natural lake and the overall fate of PAEs in lake ecosystem were given. The concentrations of the Sigma(13)PAEs in atmospheric particles were at a significantly low level ranging from 2740 to 11,890 pg.m(-3) and 2622 to 15,331 pg.m(-3) in ZM (the lakeshore site) and HB (the downtown site), respectively. There were no statistically significant differences of PAEs between ZM and HB. The highest atmospheric PAE concentrations in August were likely related to the long-range transport from Guangdong Province. Di(2-ethylhexyl) phthalate (DEHP), diisobutyl phthalate (DIBP) and dibutyl phthalate (DBP) were the main PAE congeners. Temporally, DIBP and DBP had the highest fractions in winter and the lowest fractions in summer. It might be justified by the condensation of DIBP and DBP from gas phase to particulate phase at low temperature. Multimedia comparison of PAE profiles in Lake Choahu revealed that low molecular weight (LMW) congeners were transported mainly through water while high molecular weight (HMW) congeners were transported mainly through atmosphere.
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Children's toys are made of artificial material often softened by phthalates. These are synthetic compounds added to PVC as plasticizers for the purpose of improving its elasticity and flexibility. Phthalates can endanger the health of children exposed to their effect by inducing reproductive, hormonal and developmental disorders. The goal of the present study was to determine phthalate presence in children's toys and childcare articles from different sources sold in different areas in Croatia in 2012 and 2013. Diisononyl phthalate, di(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate, diisodecyl phthalate, di-n-octyl phthalate and butylbenzyl phthalate were included in the analysis. About 60% of the toys analysed contained plastic; up to 20% had detectible levels of phthalates, 94-96% containing toxic DEHP. Over 60% contained DEHP at concentrations more than 10 times than that permitted, mostly dolls and toy animals. The percentage of toys containing phthalates was higher in 2013 in comparison to 2012. We discuss the availability and similarities in composition of phthalates by comparing our results with reports from other countries.
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Quantifying the spatio-temporal distribution of arthropods in tropical rainforests represents a first step towards scrutinizing the global distribution of biodiversity on Earth. To date most studies have focused on narrow taxonomic groups or lack a design that allows partitioning of the components of diversity. Here, we consider an exceptionally large dataset (113,952 individuals representing 5,858 species), obtained from the San Lorenzo forest in Panama, where the phylogenetic breadth of arthropod taxa was surveyed using 14 protocols targeting the soil, litter, understory, lower and upper canopy habitats, replicated across seasons in 2003 and 2004. This dataset is used to explore the relative influence of horizontal, vertical and seasonal drivers of arthropod distribution in this forest. We considered arthropod abundance, observed and estimated species richness, additive decomposition of species richness, multiplicative partitioning of species diversity, variation in species composition, species turnover and guild structure as components of diversity. At the scale of our study (2km of distance, 40m in height and 400 days), the effects related to the vertical and seasonal dimensions were most important. Most adult arthropods were collected from the soil/litter or the upper canopy and species richness was highest in the canopy. We compared the distribution of arthropods and trees within our study system. Effects related to the seasonal dimension were stronger for arthropods than for trees. We conclude that: (1) models of beta diversity developed for tropical trees are unlikely to be applicable to tropical arthropods; (2) it is imperative that estimates of global biodiversity derived from mass collecting of arthropods in tropical rainforests embrace the strong vertical and seasonal partitioning observed here; and (3) given the high species turnover observed between seasons, global climate change may have severe consequences for rainforest arthropods.
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This study reports an analytical approach intended to be used for investigation of non-targeted environmental contaminants and to characterize the organic pollution pattern of bee wax comb samples. The method comprises a generic extraction followed by detection with gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC-TOF-MS), operated in electron impact ionization (EI) mode. The screening approach for the investigation of non-targeted contaminants consisted of initial peak detection by deconvolution and matching the first-stage mass spectra EI-MS(1) with a nominal mass spectral library. To gain further confidence in the structural characterization of the contaminants under investigation, the molecular formula of representative ions (molecular ion when present in the EI spectrum) and, for at least other two fragment ions, was provided for those with an accurate mass scoring (mass error < 5 ppm). This methodology was applied for screening environmental contaminants in 50 samples of bee wax comb. This approach has allowed the tentative identification of some GC-amenable contaminants belonging to different chemical groups, among them, phthalates and polycyclic aromatic hydrocarbons (PAHs), along with residues of veterinary treatments used in apiculture.
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In this study, conducted in French Guiana, a part of the native range of the fire ant Solenopsis saevissima, we compared the cuticular hydrocarbon profiles of media workers with previous results based on intraspecific aggressiveness tests. We noted a strong congruence between the two studies permitting us to delimit two supercolonies extending over large distances (up to 54 km), a phenomenon known as unicoloniality. Solenopsis geminata workers, taken as an out-group for cluster analyses, have a very different cuticular hydrocarbon profile. Because S. saevissima has been reported outside its native range, our conclusion is that this species has the potential to become invasive because unicoloniality (i.e., the main attribute for ants to become invasive) was shown at least for the Guianese population. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.
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In tropical wet forests, ants are a large proportion of the animal biomass, but the factors determining abundance are not well understood. We characterized ant abundance in the litter layer of 41 mature wet forest sites spread throughout Central America (Chiapas, Guatemala, Honduras, Nicaragua, and Costa Rica) and examined the impact of elevation (as a proxy for temperature) and community species richness. Sites were intentionally chosen to minimize variation in precipitation and seasonality. From sea level to 1500 m ant abundance very gradually declined, community richness declined more rapidly than abundance, and the local frequency of the locally most common species increased. These results suggest that within this elevational zone, density compensation is acting, maintaining high ant abundance as richness declines. In contrast, in sites above 1500 m, ant abundance dropped abruptly to much lower levels. Among these high montane sites, community richness explained much more of the variation in abundance than elevation, and there was no evidence of density compensation. The relative stability of abundance below 1500 m may be caused by opposing effects of temperature on productivity and metabolism. Lower temperatures may decrease productivity and thus the amount of food available for consumers, but slower metabolisms of consumers may allow maintenance of higher biomass at lower resource supply rates. Ant communities at these lower elevations may be highly interactive, the result of continuous habitat presence over geological time. High montane sites may be ephemeral in geological time, resulting in non-interactive communities dominated by historical and stochastic processes. Abundance in these sites may be determined by the number of species that manage to colonize and/or avoid extinction on mountaintops.
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We live amid a global wave of anthropogenically driven biodiversity loss: species and population extirpations and, critically, declines in local species abundance. Particularly, human impacts on animal biodiversity are an under-recognized form of global environmental change. Among terrestrial vertebrates, 322 species have become extinct since 1500, and populations of the remaining species show 25% average decline in abundance. Invertebrate patterns are equally dire: 67% of monitored populations show 45% mean abundance decline. Such animal declines will cascade onto ecosystem functioning and human well-being. Much remains unknown about this “Anthropocene defaunation”; these knowledge gaps hinder our capacity to predict and limit defaunation impacts. Clearly, however, defaunation is both a pervasive component of the planet’s sixth mass extinction and also a major driver of global ecological change.
Phthalate esters are one of the most frequently detected persistent organic pollutants in the environment. A better understanding of their occurrence and degradation in the environment and during wastewater treatment processes will facilitate the development of strategies to reduce these pollutants and to bioremediate contaminated freshwater and soil. Phthalate esters occur at measurable levels in different environments worldwide. For example, the concentrations of dimethyl phthalate (DMP) in atmospheric particulate matter, fresh water and sediments, soil, and landfills are N.D.-10.4ng/m(3), N.D.-31.7μg/L, N.D.-316μg/kg dry weight, and N.D.-200μg/kg dry weight, N.D.-43.27μg/L, respectively. Bis(2-ethylhexyl) phthalate (DEHP) and di-n-butyl phthalate (DBP) are primary phthalate ester pollutants. Urbanization has increased the discharge of phthalate esters to atmospheric and aquatic environments, and the use of agricultural plastics has exacerbated soil contamination by phthalate esters in rural areas. Aerobic biodegradation is the primary manner of phthalate ester mineralization in the environment, and this process has been widely studied. Phthalate esters can be removed during wastewater treatment processes. The combination of different wastewater treatment technologies showed greater efficiency in the removal of phthalate esters than individual treatment steps, such as the combination of anaerobic wastewater treatment with a membrane bioreactor would increase the efficiency of phthalate ester removal from 65%-71% to 95%-97%. This review provides a useful framework to identify future research objectives to achieve the mineralization and elimination of phthalate esters in the environment.