Persistent Organic Pollutants in gull eggs of two species (Larus michahellis and Larus audouinii) from the Ebro delta Natural Park

The aim of this study was to determine the impact of priority and emerging Persistent Organic Pollutants (POPs) in gull eggs from two species, the scavenger Larus michahellis and the protected species, Larus audouinii. These two species share habitat in the Natural Park of the Ebro delta (Catalonia, Spain). Compounds studied are included or under consideration in the Stockholm Convention and comprise polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorinated compounds (OCs), perfluorinated compounds (PFCs) and short chain chlorinated paraffins (SCCPs). Four methods based in selective extraction and gas or liquid chromatography coupled to mass spectrometry were used and quality parameters are provided. OC pesticides and marker PCBs were the most abundant chemical families detected in eggs from the two species, followed by PFCs, PBDEs (especially BDE 209) and SCCPs. Dioxin-like PCBs and PCDD/Fs were also detected in all samples. The overall widespread presence of POPs is discussed in terms of feeding habits, bird ecology and anthropogenic pressures in the protected Ebro delta breeding area.     

Modeling the dynamics of DDT in a remote tropical floodplain: indications of post-ban use?

Significant knowledge gaps exist regarding the fate and transport of persistent organic pollutants like dichlorodiphenyltrichloroethane (DDT) in tropical environments. In Brazil, indoor residual spraying with DDT to combat malaria and leishmaniasis began in the 1950s and was banned in 1998. Nonetheless, high concentrations of DDT and its metabolites were recently detected in human breast milk in the community of Lake Puruzinho in the Brazilian Amazon. In this work, we couple analysis of soils and sediments from 2005 to 2014 at Puruzinho with a novel dynamic floodplain model to investigate the movement and distribution of DDT and its transformation products (dichlorodiphenyldichloroethylene (DDE) and dichlorodiphenyldichloroethane (DDD)) and implications for human exposure. The model results are in good agreement with the accumulation pattern observed in the measurements, in which DDT, DDE, and DDD (collectively, DDX) accumulate primarily in upland soils and sediments. However, a significant increase was observed in DDX concentrations in soil samples from 2005 to 2014, coupled with a decrease of DDT/DDE ratios, which do not agree with model results assuming a post-ban regime. These observations strongly suggest recent use. We used the model to investigate possible re-emissions after the ban through two scenarios: one assuming DDT use for IRS and the other assuming use against termites and leishmaniasis. Median DDX concentrations and p,p′-DDT/p,p′-DDE ratios from both of these scenarios agreed with measurements in soils, suggesting that the soil parameterization in our model was appropriate. Measured DDX concentrations in sediments were between the two re-emission scenarios. Therefore, both soil and sediment comparisons suggest re-emissions indeed occurred between 2005 and 2014, but additional measurements would be needed to better understand the actual re-emission patterns. Monte Carlo analysis revealed model predictions for sediments were very sensitive to highly uncertain parameters associated with DDT degradation and partitioning. With this model as a tool for understanding inter-media cycling, additional research to refine these parameters would improve our understanding of DDX fate and transport in tropical sediments.     

Morphological,compositional and ultrastructural changes in the Scrobicularia plana shell in response to environmental mercury – An indelible fingerprint of metal exposure?

The study aimed to assess morphological, structural and compositional alterations in Scrobicularia plana nacre environmentally exposed to mercury in order to seek out the possibility of the assessed alterations as a monitoring tool to handle complexity and interactions of metals in the environment involving a non-invasive methodology. Bivalves were collected from a mercury contaminated site (Laranjo basin – Ria de Aveiro, Portugal) and a reference site in the same aquatic system. The combination of scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS) technique depicted a sheet like morphology of bivalve nacre collected from the reference site. Moreover, EDS plot exhibited the presence of potassium, oxygen, calcium, and carbon elements. Shells collected from the contaminated area depicted lamellar patches like structures with particle like morphology composition. SEM images corresponding to the elemental analysis by EDS plot clearly denoted the presence of mercury. SEM images from the other locations of the contaminated shells depicted large surface area, a broken or ruptured symmetry of organic matrix as well as crack-like gaps. The influence of environmental mercury affecting the surface morphology of S. plana nacre showed dimple like morphology (as proved by transmission electron microscopy, TEM). The possible explanation may be the replacement of calcium elements with other elements or alloys from the nacre composite collected from contaminated region. Therefore, the nacre fingerprint may be useful as innovative knowledge and applicable tool aiming at risk reduction from noxious mercury present in the environment. Overall results suggested the use of shell as an indelible fingerprint of metal exposure.     

Analytical methods and validation for determining trace elements in red wines

The objective of this work is to quantify As, Hg, Cd, Ni and Pb in Portuguese red wines. First, the methods for the quantification of trace elements in red wines were validated. Several pre-treatments were compared, namely a pre-digestion process with HNO₃, a pre-oxidation step with H₂O₂, and a spiking step of wine samples with a known concentration of the trace elements analyzed. Except for As, it was determined that the quantification of the trace elements does not require a pre-digestion process with HNO₃. For all of the trace elements analyzed, a pre-oxidation step with H₂O₂ may enable an accurate quantification. The techniques chosen for the quantification of trace elements were hydride generation atomic absorption spectrometry (HGAAS) for As and Hg, electrothermal atomic absorption spectrometry (ETAAS) for Cd, and flame atomic absorption spectrometry (FAAS) for Ni and Pb. In the second stage of this work, 25 Portuguese red wines spanning all of the red wine-producing regions were analyzed for all of the five trace elements referred to above. Only Cd and Pb have shown concentrations above the limit values defined by the “Organization Internationale de la Vigne et du Vin.” The Target Hazard Quotient (THQ) equation was used to determine in which wine-producing regions that wine consumption can be a problem for public health in terms of the concentrations of the five trace elements analyzed. THQ values have indicated that for the universe of the 25 red wines analyzed no region produces wines that can pose problems for public health, when the Portuguese red wine standard consumption is considered.     

Evaluation of genotoxicity and coumarin production in conventional and organic cultivation systems of Mikania glomerata Spreng

Abstract

Mikania glomerata Sprengel, popularly known as “guaco,” is used in Brazilian folk medicine for several inflammatory and allergic conditions. Besides, the popular use “guaco” is indicated by the Brazilian Ministry of Health as a safe and effective herbal medicine. The biological activity of M. glomerata extracts is due to the presence of the coumarins, a large family of phenolic substances found in plants and is made of fused benzene and α-pyrone rings. Considering that there are few data on the biological effects of the extracts of M. glomerata, mainly in genetic level, this work aims to evaluate, in vitro, the genotoxicity and coumarin production in M. glomerata in conventional and organic growing. The data showed that the organic culture system showed double the concentration of coumarin being significantly more productive than the conventional system. Besides, the results of comet assay suggest that extracts of M. glomerata cultivated in a conventional system was genotoxic, increased DNA damage levels while the organic extracts seem to have antigenotoxic effect possibly due to the concentration of coumarins. Additional biochemical investigations are necessary to elucidate the mechanisms of action of M. glomerata extracts, which were found to have a role in protection against DNA damage.     

Pine needles as passive bio-samplers to determine polybrominated diphenyl ethers

Eight polybrominated diphenyl ethers (PBDEs) were determined in pine needles of three species (Pinus halepensis, Pinus pinea and Pinus nigra) collected in the NE Spain in an attempt to use this matrix for the biomonitoring of airborne PBDEs. The method used was based in ultrasonic extraction followed by alumina and Florisil clean-up and determination by gas chromatography coupled to mass spectrometry in negative chemical ionization. Recoveries were between 99% and 138%, limits of detection between 0.011 and 0.070 ng g⁻¹-dw (0.232 ng g⁻¹-dw for BDE 209) and repeatability lower than 13%. PBDE levels ranged between 0.027 ng g⁻¹-dw and 13.04 ng g⁻¹-dw, with predominance of BDE 209, followed by BDEs 47. P. halepensis was the species with the highest PBDE levels and P. nigra, the least, according to their widespread and remote distribution, respectively. The presence of PBDEs in pine needles was attributed to the release of in-use PBDEs, transport through atmosphere and adsorption upon lipid rich pine needles. Given the easy collection of pine needles, its ample distribution and its potential to accumulate airborne contaminants, this matrix is proposed as passive bio-sampler to be used in PBDE monitoring programs.

Capsule

Pine needles can be used to biomonitor airborne PBDEs.     

Increase of 210Po levels in human semen fluid after mussel ingestion

Polonium-210 (²¹⁰Po) radioactive concentrations were determined in human semen fluid of vasectomized non-smoker volunteers. The ²¹⁰Po levels ranged from 0.10 to 0.39 mBq g⁻¹ (mean: 0.23 ± 0.08 mBq g⁻¹). This value decreased to 0.10 ± 0.02 mBq g⁻¹ (range from 0.07 to 0.13 mBq g⁻¹) after two weeks of a controlled diet, excluding fish and seafood. Then, volunteers ate during a single meal 200 g of the cooked mussel Perna perna L., and ²¹⁰Po levels were determined again, during ten days, in semen fluid samples collected every morning. Volunteers continued with the controlled diet and maintained sexual abstinence through the period of the experiment. A 300% increase of ²¹⁰Po level was observed the day following mussel consumption, with a later reduction, such that the level returned to near baseline by day 4.     

Modelling the extraction of soil contaminants with supercritical carbon dioxide

Extractions of volatile organic compounds (VOC’s) in contaminated soil from petroleum site were performed with supercritical carbon dioxide at different temperatures, pressures, extraction times, solvent flow rates, soil moisture contents and soil acidity. Three soil systems were investigated in order to compare the best parameters for extraction. A central composite rotatable design has been used to evaluate the influence of operation conditions on the extraction efficiency to generate model equations representing the types of soil. The results indicate that at least 70-80% of the initial amount of VOC’s can be removed at moderate temperatures even at very high moisture content. Supercritical extraction is best suited to silt type soils which have a low adsorption capacity. VOC’s recoveries from the artificial contaminated soil samples were higher in comparison with real contaminated soils. At moderate temperatures, the extraction efficiency for real soils is low because pollutants bind strongly to the soil.     

Integrated spatiotemporal trends using TRMM 3B42 data for the Upper São Francisco River basin,Brazil

Trend analysis is an important issue for the decision-making processes. Thus, trends of rainfall, consecutive dry days (CDD), and consecutive wet days (CWD) in the Upper São Francisco River basin, Brazil, using daily rainfall data from the Tropical Rainfall Measuring Mission (TRMM) for recent 18 years, were analyzed. Instead of analyzing the trend of one average time series for one specific confidence level, a spatiotemporal analysis over the entire area with 169 continuous time series is done by applying the nonparametric Mann-Kendall and Sen tests for simultaneously 13 confidence levels and a new integrated confidence classification is proposed. The results show that the rainfall has increased during the less rainy periods (from June to October) and has decreased in the rainy periods (from November to May), with the highest and lowest confidence levels, respectively. An analysis of CDD and CWD shows that the number of CDD has decreased, while the number of CWD has increased, which revealed that the dry periods are more frequently interrupted for the period studied.     

Utilization of UV‐A and UV‐C radiation in advanced oxidation processes with the intention of removing color and organic matter from the gross leachate of a stabilized sanitary landfill

The present work investigated color and biochemical oxygen demand (COD) removal from treated landfill leachate via advanced oxidative processes (AOPs) artificially emitted. The AOP H₂O₂/UV, TiO₂/UV, and photolysis were tested in two bench‐scale photoreactors: The first one with UV‐C lamp and the other with UV‐A lamp associated or not with coagulation / flocculation pretreatment. Crude leachate samples with pH ranging from 8 to 3 were used, and time varied in 30, 45, and 60 minutes. Experiments were performed in two stages: step 1 with a 20 mL volume from each sample and step 2 with repetition of the best results from the previous step, adopting the 150 mL volume. In step 1, the AOP applied in the crude leachate sample showed the best results, standing out H₂O₂/UV‐C with 30 minutes and TiO₂/UV‐A with 60 minutes. In step 2, H₂O₂/UV‐C had a 60% color removal and 25% COD reduction, while TiO₂/UV‐A had a 10% color removal and 20% COD reduction. Therefore, the H₂O₂/UV‐C process was the most efficient, because the complex characteristics of the effluent interfered in the TiO₂/UV‐A efficiency, but it is necessary to eliminate the process interferences. The use of artificial radiation is a viable alternative; however, it can be costly, being relevant in the associations between processes with artificial UV and solar UV, as the natural radiation becomes more attractive and allows the process operating costs reduction.