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.     

PAHs in water and surface sediments from Douro River estuary and Porto Atlantic coast (Portugal)—impacts on human health

This study investigated the presence of 16 priority polycyclic aromatic compounds (PAHs) in waters from the Douro River estuary and nearby Atlantic seacoast, which both bath the Porto metropolis. In the area, there is an oil refinery, an important harbour, an intense maritime traffic, small marinas and highly inhabited cities. For the analysis of PAHs, water samples were taken from four sampling sites, at six different times of the year (2011), and extracted by solid-phase extraction (dissolved fraction) and by ultrasound technique (suspended fraction), before their quantification by gas chromatography–mass spectrometry. Results not only proved the ubiquitous distribution of all analysed PAHs in the present habitat, but also that their global amounts (∑₁₆PAHs) were extremely high at all sampling sites. Their average concentrations attained ≈ 55 ng/L and ≈ 52 μg/g dry weight (dw), respectively, in water and surface sediments. Accordingly, the surveyed area was classified as highly polluted by these organics and so, in view of the concentrations, mutagenic/carcinogenic responses in both humans and aquatic animals are possible to occur. The percentages of carcinogenic PAHs for humans (group 1) dissolved in water and in surface sediments were ca. 5 and 6%, respectively. These results are the first reported in the area and can be used as a baseline for future control of the PAHs levels locally while serving the building of global scenarios of PAHs pollution in Europe.

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Graphical abstract Percentage of PAHs, from different categories acordingly to WHO (2016), in both surface sediments and surface waters from Douro River estuary and Porto Atlantic seacoast; group 1 - carcinogenic, group 2A - probably carcinogenic, group 2B - possibly carcinogenic, and group 3 - not classifiable as carcinogenic to humans

     

Air-quality modelling in the Lake Baikal region

In this paper, we assess the status of the air quality in the Lake Baikal region which is strongly influenced by the presence of anthropogenic pollution sources. We combined the local data, with global databases, remote sensing imagery and modelling tools. This approach allows to inventorise the air-polluting sources and to quantify the air-quality concentration levels in the Lake Baikal region to a reasonable level, despite the fact that local data are scarcely available. In the simulations, we focus on the month of July 2003, as for this period, validation data are available for a number of ground-based measurement stations within the Lake Baikal region.     

Assessment of solar driven TiO2-assisted photocatalysis efficiency on amoxicillin degradation

The objective of this work was to evaluate the efficiency of a solar TiO₂-assisted photocatalytic process on amoxicillin (AMX) degradation, an antibiotic widely used in human and veterinary medicine. Firstly, solar photolysis of AMX was compared with solar photocatalysis in a compound parabolic collectors pilot scale photoreactor to assess the amount of accumulated UV energy in the system (Q _UV) necessary to remove 20 mg L^?1 AMX from aqueous solution and mineralize the intermediary by-products. Another experiment was also carried out to accurately follow the antibacterial activity against Escherichia coli DSM 1103 and Staphylococcus aureus DSM 1104 and mineralization of AMX by tracing the contents of dissolved organic carbon (DOC), low molecular weight carboxylate anions, and inorganic anions. Finally, the influence of individual inorganic ions on AMX photocatalytic degradation efficiency and the involvement of some reactive oxygen species were also assessed. Photolysis was shown to be completely ineffective, while only 3.1 kJ_UV?L^?1 was sufficient to fully degrade 20 mg L^?1 AMX and remove 61 % of initial DOC content in the presence of the photocatalyst and sunlight. In the experiment with an initial AMX concentration of 40 mg L^?1, antibacterial activity of the solution was considerably reduced after elimination of AMX to levels below the respective detection limit. After 11.7 kJ_UV?L^?1, DOC decreased by 71 %; 30 % of the AMX nitrogen was converted into ammonium and all sulfur compounds were converted into sulfate. A large percentage of the remaining DOC was in the form of low molecular weight carboxylic acids. Presence of phosphate ions promoted the removal of AMX from solution, while no sizeable effects on the kinetics were found for other inorganic ions. Although the AMX degradation was mainly attributed to hydroxyl radicals, singlet oxygen also plays an important role in AMX self-photosensitization under UV/visible solar light.     

Bulk atmospheric deposition of persistent toxic substances (PTS) along environmental gradients in Brazil

Bulk atmospheric deposition measurements for selected persistent toxic substances (PTS) were performed along environment gradients (urban–suburban–rural–background sites) in Brazil. The aim with this work is to investigate the fate of PTS and their emissions in South America, particularly along environment transects. Bulk sampler systems (polyurethane foams, 1?×?1 m²) were fixed along environment gradients (urban–suburban–rural–background) over summer and winter periods (2005–2007) at sites of different climate zones of Brazil. Organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) were analyzed by gas chromatography coupled to electron capture detector (Shimadzu 2010, 20i GC-ECD). Urban sites reported the highest deposition rates for all PTS, ranging from tens to thousands of pictograms per square meter per day. Basically, there were no obvious seasonal differences in deposition rate concentrations for PTS along the urban–suburban–rural–background gradient. Dichlorodiphenyltrichloroethane (DDT) and its metabolites were the OCs most frequently detected at relatively high deposition rate levels (>1,000 pg m^?2 day^?1). Other legacy and current-use pesticides such as hexachlorocyclohexanes, endosulfans, hexachlorcyclobenzine, dieldrin, aldrin, metoxichlor, and chlodanes were also detected at lower deposition rate levels (10–100 pg m^?2 day^?1). PCBs were detected at extremely high deposition rate levels (1,000–10,000 pg m^?2 day^?1) with highest contributions from the tetra-PCBs (PCB-52, PCB-44, PCB-66, PCB-81, and PCB-77) and penta-PCB congeners (PCB-101, PCB-105, PCB-114, PCB-118, and PCB-126). The greatest deposition rate concentrations for total PCBs were mainly detected at urban sites in connection with high population densities. The observed high deposition rate concentrations for PCBs and DDTs at urban sites are probably associated with old PTS stocks emissions. For PCBs in particular, the high levels are strongly associated with local population densities, highlighting the effect of local/regional urban sources on these target PTS. These results are important to show that even though the use of PTS is regulated, the deposition of selected PTS is still impacted by local and regional emissions in Brazil and may be related to the historical and continued emissions from old PTS stocks.     

Influence of pleat geometry on filter cleaning in PTFE/glass composite filter

A pleated filter bag is often used to treat exhaust gas in many industrial applications, due to its fairly high dust collection efficiency and relatively low pressure drop. This work deals with the optimum pleating geometries of a pleated filter made with a newly developed PTFE/glass composite filter. It was found that pleating geometries, including pleat height and pleat pitch, directly affect the cleaning efficiency. The design index, α, which stands for the ratio of pleat height to pleat pitch, is 1.48 for optimum operation. When the α value was higher than 1.48, the pressure drop across the pleated filter medium increased, resulting in a decreased cleaning interval due to the difficulty of filter cleaning. Therefore, it is necessary that the optimum pleating geometry should be determined by employing the dimensionless parameter, α, in the design of cartridge filters.

Implications: A pleated filter bag is often used to treat exhaust gas in many industrial applications due to its fairly high dust collection efficiency and relatively low pressure drop. The present paper introduces an optimum design configuration to make a pleated filter with newly developed PTFE/glass composite filter media. A dimensionless parameter that is the ratio of pleat height to pleat pitch should be considered to make the best quality pleated filter.     

Behavioural determinants of gene flow in the bat Miniopterus schreibersii

Dispersal and migratory behaviours are often important determinants of gene flow in wild species, and we have studied their role using ringing-recapture data in the Portuguese population of Miniopterus schreibersii, a cave-dwelling bat that forms large maternity colonies. Juvenile dispersal, usually a major agent of gene flow, appears to be negligible, as young females never settled to give birth in foreign colonies. Likewise, there was virtually no dispersal of adult females to foreign maternity colonies. This strong philopatry virtually eliminated female-mediated gene flow, but we found a great potential for male-mediated gene flow among colonies, as regional migrations temporarily joined both sexes from different colonies in the same roosts, during the mating season. In fact, females from some colonies were more likely to mate with males from foreign colonies than from their own, thus potentially bringing home genes of foreign males. In spite of this abundant gene flow, we found a pattern of isolation by distance and even strong barriers to gene flow, which is explained by the fact that migrations were usually too short to allow direct flow among distant colonies. We concluded that potential gene flow is influenced by the distance between colonies and the availability of mating roosts between them. In addition, we found this flow to be asymmetrical, with a dominant direction from the largest to the smallest colonies. Our ringing-recapture estimates of potential gene flow based on dispersal and migratory behaviour are compatible with the genetic structure of the population for both nuclear and mitochondrial DNA. Our conclusions have implications for the conservation of bats with a spatial behaviour similar to that of M. schreibersii. Colonies should be managed individually because strict female philopatry not only promotes their isolation but also minimises the contribution of immigration in rescuing declining colonies. Furthermore, the results underline the importance of preserving mating roosts to maintain gene flow among colonies.     

A Screening-Level Assessment of Lead, Cadmium, and Zinc in Fish and Crayfish from Northeastern Oklahoma, USA

The objective of this study was to evaluate potential human and ecological risks associated with metals in fish and crayfish from mining in the Tri-States Mining District (TSMD). Crayfish (Orconectes spp.) and fish of six frequently consumed species (common carp, Cyprinus carpio; channel catfish, Ictalurus punctatus; flathead catfish, Pylodictis olivaris; largemouth bass, Micropterus salmoides; spotted bass, M. punctulatus; and white crappie, Pomoxis annularis) were collected in 2001--2002 from the Oklahoma waters of the Spring River (SR) and Neosho River (NR), which drain the TSMD. Samples from a mining-contaminated site in eastern Missouri and from reference sites were also analyzed. Individual fish were prepared for human consumption in the manner used locally by Native Americans (headed, eviscerated, and scaled) and analyzed for lead, cadmium, and zinc. Whole crayfish were analyzed as composite samples of 5--60 animals. Metals concentrations were typically higher in samples from sites most heavily affected by mining and lowest in reference samples. Within the TSMD, most metals concentrations were higher at sites on the SR than on the NR and were typically highest in common carp and crayfish than in other taxa. Higher concentrations and greater risk were associated with fish and crayfish from heavily contaminated SR tributaries than the SR or NR mainstems. Based on the results of this and previous studies, the human consumption of carp and crayfish could be restricted based on current criteria for lead, cadmium, and zinc, and the consumption of channel catfish could be restricted due to lead. Metals concentrations were uniformly low in Micropterus spp. and crappie and would not warrant restriction, however. Some risk to carnivorous avian wildlife from lead and zinc in TSMD fish and invertebrates was also indicated, as was risk to the fish themselves. Overall, the wildlife assessment is consistent with previously reported biological effects attributed to metals from the TSMD. The results demonstrate the potential for adverse effects in fish, wildlife, and humans and indicate that further investigation of human health and ecological risks, to include additional exposure pathways and endpoints, is warranted.This study was conducted by the Columbia Environmental Research Center (CERC) of the U.S. Geological Survey (USGS) and cooperating organizations and government agencies. All field and laboratory procedures conformed to the “Guidelines for the use of fishes in research” of the American Fisheries Society (AFS), Institute of Fishery Research Biologists (AIFRB), and American Society of Ichthyologists and Herpetologists (ASIH) Use of Fishes in Research Committee (AFS, AIFRB, and ASIH 2004), and with all USGS and CERC guidelines for the humane treatment of test organisms during culture and experimentation. Use of trade names does not constitute USGS or U.S. government endorsement.     

Emission of polycyclic aromatic hydrocarbons from gasohol and ethanol vehicles

The exhaust emission of the polycyclic aromatic hydrocarbons (PAHs) considered toxic to human health were investigated on two spark ignition light duty vehicles, one being gasohol (Gasohol, in Brazil, is the generic denomination for mixtures of pure gasoline plus 20–25% of anhydrous ethyl alcohol fuel (AEAF).)-fuelled and the other a flexible-fuel vehicle fuelled with hydrated ethanol. The influence of fuel type and quality, aged lubricant oil type and use of fuel additives on the formation of these compounds was tested using standardized tests identical to US FTP-75 cycle. PAH sampling and chemical analysis followed the basic recommendations of method TO-13 (United States. Environmental Protection Agency, 1999. Compendium Method TO-13A – Determination of polycyclic Aromatic hydrocarbons (PAH) in Ambient Air Using Gas Chromatography/Mass Spectrometry (CG/MS). Center for environmental research information, Cincinnati, p. 78), with the necessary modification for this particular application.Results showed that the total PAH emission factor varied from 41.9 μg km^?1 to 612 μg km^?1 in the gasohol vehicle, and from 11.7 μg km^?1 to 27.4 μg km^?1 in the ethanol-fuelled vehicle, a significant difference in favor of the ethanol vehicle. Generally, emission of light molecular weight PAHs was predominant, while high molecular weights PAHs were not detected. In terms of benzo(a)pyrene toxicity equivalence, emission factors varied from 0.00984 μg TEQ km^?1 to 4.61 μg TEQ km^?1 for the gasohol vehicle and from 0.0117 μg TEQ km^?1 to 0.0218 μg TEQ km^?1 in the ethanol vehicle.For the gasohol vehicle, results showed that the use of fuel additive causes a significant increase in the emission of naphthalene and phenanthrene at a confidence level of 90% or higher; the use of rubber solvent on gasohol showed a reduction in the emission of naphthalene and phenanthrene at the same confidence level; the use of synthetic oil instead of mineral oil also contributed significantly to a decrease in the emission of naphthalene and fluorene. In relation to the ethanol vehicle, the same factors were tested and showed no statistically significant influence on PAH emission.