Spatial distribution and quantification of endocrine-disrupting chemicals in Sado River estuary, Portugal

The important Portuguese Sado River estuary has never been investigated for the presence of potentially endocrine-disrupting chemicals (EDCs), such as natural estrogens (estradiol, estrone), pharmaceutical estrogens (17α-ethynylestradiol), phytoestrogens (daidzein, genistein and biochanin A), or industrial chemicals (4-octylphenol, 4-nonylphenol, and bisphenol A). Thus, the main objective of this study was to evaluate their presence at 13 sampling points distributed between both the industrial and the natural reserve areas of the estuary, zones 1 and 2, respectively. For that, water samples collected in summer and winter were processed by solid phase extraction and analyzed by high-performance liquid chromatography with photodiode array detection and gas chromatography–mass spectroscopy. Results showed that estrone, ethynylestradiol, all the aforementioned phytoestrogens as well as bisphenol A and 4-octylphenol were found in zone 1. In zone 2, neither estrogens nor 4-OP were found. However, in the same zone, daidzein (500 ng/L) and genistein (320 ng/L) attained their highest levels in summer, whereas biochanin A peaked in winter (170 ng/L). Furthermore, bisphenol A was also found in some areas of zone 2, but showed similar concentrations in both surveys (about 220 ng/L). This study demonstrated that the Sado River estuary had low EDCs levels, suggesting that the Sado’s high hydrodynamic activity may be involved in the dilution of local pollution. It was suggested that at the current levels of concentrations, all assayed EDCs are unlikely to individually cause endocrine disruption in local animals. However, under a continuous exposure scenario, an additive and/or synergistic action of the estrogenic chemicals load can not be excluded, and so, continuous monitoring is advisable.     

A new <Emphasis Type="Italic">P. putida</Emphasis> instrumental toxicity bioassay

Here, we present a new toxicity bioassay (CO₂-TOX), able to detect toxic or inhibitory compounds in water samples, based on the quantification of Pseudomonas putida KT2440 CO₂ production. The metabolically produced CO₂ was measured continuously and directly in the liquid assay media, with a potentiometric gas electrode. The optimization studies were performed using as a model toxicant 3,5-DCP (3,5-dichlorophenol); later, heavy metals (Pb²⁺, Cu²⁺, or Zn²⁺) and a metalloid (As⁵⁺) were assayed. The response to toxics was evident after 15 min of incubation and at relatively low concentrations (e.g., 1.1 mg/L of 3,5-DCP), showing that the CO₂-TOX bioassay is fast and sensitive. The EC₅₀ values obtained were 4.93, 0.12, 6.05, 32.17, and 37.81 mg/L for 3,5-DCP, Cu²⁺, Zn²⁺, As⁵⁺, and Pb²⁺, respectively, at neutral pH. Additionally, the effect of the pH of the sample and the use of lyophilized bacteria were also analyzed showing that the bioassay can be implemented in different conditions. Moreover, highly turbid samples and samples with very low oxygen levels were measured successfully with the new instrumental bioassay described here. Finally, simulated samples containing 3,5-DCP or a heavy metal mixture were tested using the proposed bioassay and a standard ISO bioassay, showing that our test is more sensible to the phenol but less sensible to the metal mixtures. Therefore, we propose CO₂-TOX as a rapid, sensitive, low-cost, and robust instrumental bioassay that could perform as an industrial wastewater-process monitor among other applications.     

Role of carbonyls and aromatics in the formation of tropospheric ozone in Rio de Janeiro,Brazil

The ozone in Rio de Janeiro has been in violation of national air quality standards. Among all of the monitoring stations, the Bangu neighbourhood has the most violations of the national standard of 160 μg m^?3 for the years 2012 and 2013. This study evaluated the reactivity of the carbonyls and aromatics in the tropospheric ozone formation processes. The samples were collected between July and October of 2013. Carbonyls were sampled using SiO₂ cartridges coated with C₁₈ and impregnated with 2,4-dinitrophenylhydrazine and were analysed by HPLC. Activated carbon cartridges and GC/MS were used to measure the concentration of monoaromatic hydrocarbons. An air quality monitoring station provided the concentrations of the criteria pollutants and the meteorological parameters. Cluster analysis and a Pearson correlation matrix were used to determine the formation of groups and the correlation of the variables. The evaluation of the volatile organic compounds (VOC) reaction with OH radicals and the MIR scale was used to extrapolate the reactivity of VOCs to the ozone formation. The average concentrations obtained were 19.7 and 51.9 μg m^?3 for formaldehyde and acetaldehyde, respectively. The mean concentrations obtained for aromatics were 1.5, 6.7, 1.5, 2.6 and 1.6 μg m^?3 for benzene, toluene, ethyl benzene, m+p-xylene and o-xylene, respectively. The cluster analysis indicated the presence of three similar groups, with one formed by gaseous criteria pollutants, another formed by the meteorological parameters, ozone and fine particles, and the last group formed by the aromatics. For the two reactivity scales evaluated, acetaldehyde and toluene were the main ozone precursors.     

The use of oxygen consumption and ammonium excretion to evaluate the toxicity of cadmium on Farfantepenaeus paulensis with respect to salinity

The main purpose of the present study was to detect the acute toxicity of cadmium (Cd) in F. paulensis and to investigate its effect on oxygen consumption and ammonium excretion different salinities. First, we examined the acute toxicity of Cd in F. paulensis at 24, 48, 72, and 96-h lethal concentration (LC50). Cd was significantly more toxic at 5 salinity than at 20 and 36. The oxygen consumption and ammonium excretion were estimated through experiments performed on each of the twelve possible combinations of three salinities (36, 20 and 5), at temperature 20 °C. Cd showed a reduction in oxygen consumption at 5 salinity, the results show that the oxygen consumption decreases with respect to the Cd concentration. At the highest Cd concentration employed (2 mg L⁻¹), the salinity 5 and the temperature at 20 °C, oxygen consumption decreases 53.7% in relation to the control. In addition, after separate exposure to Cd, elevation in ammonium excretion was obtained, wish were 72%, 65% and 95% higher than the control, respectively. The results show that Cd is more toxic to F. paulensis at lower salinities.     

Parabens abatement from surface waters by electrochemical advanced oxidation with boron doped diamond anodes

The removal efficiency of four commonly-used parabens by electrochemical advanced oxidation with boron-doped diamond anodes in two different aqueous matrices, namely ultrapure water and surface water from the Guadiana River, has been analyzed. Response surface methodology and a factorial, composite, central, orthogonal, and rotatable (FCCOR) statistical design of experiments have been used to optimize the process. The experimental results clearly show that the initial concentration of pollutants is the factor that influences the removal efficiency in a more remarkable manner in both aqueous matrices. As a rule, as the initial concentration of parabens increases, the removal efficiency decreases. The current density also affects the removal efficiency in a statistically significant manner in both aqueous matrices. In the water river aqueous matrix, a noticeable synergistic effect on the removal efficiency has been observed, probably due to the presence of chloride ions that increase the conductivity of the solution and contribute to the generation of strong secondary oxidant species such as chlorine or HClO/ClO ⁻. The use of a statistical design of experiments made it possible to determine the optimal conditions necessary to achieve total removal of the four parabens in ultrapure and river water aqueous matrices.

     

Characterisation of black carbon-rich samples by <Superscript>13</Superscript>C solid-state nuclear magnetic resonance

There are difficulties in quantifying and characterising the organic matter (OM) in soils that contain significant amounts of partially oxidised char or charcoal materials. The anthropogenic black carbon (BC), such as that found in the Terra Preta de índio soils of the Amazon region, is a good example of the OM that is difficult to analyse in such soils. ¹³C direct polarisation/magic angle spinning (DP/MAS) at high MAS frequency, ¹H-¹³C cross polarisation (CP)/MAS with total suppression of spinning sidebands (TOSS), and chemical shift anisotropy (CSA) filter nuclear magnetic resonance techniques have been applied successfully for quantifying the different components of OM. However, because pyrogenic materials present strong local magnetic susceptibility heterogeneities, the use of CSA-filter and TOSS make the pulse sequences very sensitive to imperfections in the π pulses. In this study, the DP/MAS pulse sequence was replaced by a CP with a radio frequency ramp—variable amplitude CP (VACP)—VACP/MAS pulse sequence, and composite π pulses were used in the CSA-filter and TOSS pulse sequences. In that way, the component functionalities in a humic acid from a BC soil were successfully determined. The spectrometer time needed was greatly decreased by employing this VACP/MAS technique. This development provides an accurate method for characterising BC-rich samples from different origins.     

The Effect of UV-B Irradiation on the Biodegradability of Poly-β-Hydroxybutyrate (PHB) and Poly-ɛ-Caprolactone (PCL)

The biodegradability of poly--hydroxybutyrate and poly--caprolactone in soil compostage before and after irradiation of the polymers for 192, 425, and 600 h in a Weather-Ometer was examined. The biodegradability tests were done in soil compostage at pH 7.0, 9.0, and 11.0 to assess the influence of this parameter on degradation. The rate of degradation was directly proportional to the soil alkalinity. Poly--hydroxybutyrate showed the greatest weight loss and aging in a Weather-Ometer did not significantly increase the biodegradation, except when the polymer was aged for 425 h and buried in soil compostage of pH 11.0.     

Influences of moonlight,ambient temperature,and food availability on the diurnal and nocturnal activity of owl monkeys (<Emphasis Type="Italic">Aotus azarai</Emphasis>)

The study of activity rhythms, their potential zeitgebers and masking factors among free-ranging primates has received relatively little attention in the past. Most primates are diurnal, a few of them nocturnal, and even fewer are cathemeral. Owl monkeys (Aotus azarai azarai) regularly show diurnal, as well as nocturnal, activity in the Argentinean and Paraguayan Chaco. The goal of this study was to examine how changes in activity patterns in owl monkeys of Formosa, Argentina are related to daily, monthly, and seasonal changes in temperature, light and food availability . During 1 year, I collected activity data from five groups followed continuously from dawn to dusk, dusk to dawn or uninterruptedly during 24 or 36 h for approximately 1,500 h. I kept hourly and daily records of temperature and light conditions, and I gathered monthly information on the density, distribution and abundance of food resources available to the monkeys. I found that the area of study is highly seasonal, and characterized by significant fluctuations in rainfall, temperature, photoperiod, and food availability. Owl monkeys had on average 5 h of activity during the day and 4 h during the night. The amount of diurnal activity remained fairly constant through the year despite seasonal changes in exogenous factors. Owl monkeys did not show changes in their activity patterns that could be attributed to changes in food availability. Nocturnal activity increased as the amount of moonlight increased, whereas diurnal activity decreased following a full-moon night. Ambient temperature was a good predictor of activity only when the moon was full. These results argue convincingly for an interaction between ambient temperature and moonlight in determining the observed activity pattern. It is then highly advisable that any evaluation of diurnal activity in cathemeral animals be analyzed controlling for the possible effects of moonlight during the previous night.Communicated by P. Kappeler     

Ovarian maturation of the multi-spawning spider crab <Emphasis Type="Italic">Maja brachydactyla</Emphasis> (Decapoda: Majidae) with special reference to yolk formation

In the study of the reproductive biology of the spider crab Maja brachydactyla, the morphology of the female reproductive system and yolk formation have long been overlooked. Females spawn two or three times during their annual reproductive cycle in northern Spain (Galicia). The ovaries consist of two lobes. The right and left lobes are connected by a small cross-lobe at the level of the heart and merge at the posterior edge. Before merging, the ovaries descend to the ventral part of the body, joining the spermathecae in the vagina, which opens through a chitin tube to the gonopore, located in the sternite, at the level of the third walking leg. No morphological changes have been observed between either the different parts of the ovaries or the different annual spawning periods. At the start of vitellogenesis, the oocyte of M. brachydactyla is characterized by a large number of vesicles in the cytoplasm. These vesicles are surrounded by a unit membrane whose size increases as the oocyte matures and contain fine granular material including a variable number of ovoid, electron-dense granules. The vesicles are of diverse origin, although most of them develop directly from the mitochondria and the Golgi complex (endogenous phase of vitellogenesis). In a subsequent phase, a series of substances (principally lipoproteins) are incorporated into the ooplasma by means of micropinocytosis. These substances are also involved in yolk formation (exogenous phase of vitellogenesis). During vitellogenesis in M. brachydactyla, mitochondria play the most important role since they are not only the energetic centre of the cellule, but they also act as containers of high-energy reserve substances: the yolk granules.     

A frontier model for landscape ecology: the tapir in Honduras

We borrow a frontier specification from the econometrics literature to make inferences about the tolerance of the tapir to human settlements. We estimate the width of an invisible band surrounding human settlements which would act as a frontier or exclusion zone to the tapir to be around 290 metres.