Packed in-tube solid phase microextraction with graphene oxide supported on aminopropyl silica: Determination of target triazines in water samples

On-line in-tube solid phase microextraction (in-tube SPME) coupled to high performance liquid chromatography and tandem mass spectrometry (HPLC-MS/MS) was successfully applied to the determination of selected triazines in water samples. The method based on the employment of a packed column containing graphene oxide (GO) supported on aminopropyl silica (Si) showed that the extraction phase has a high potential for triazines extraction aiming to its physical-chemical properties including ultrahigh specific surface area, good mechanical and thermal stability and high fracture strength. Injection volume and loading time were both investigated and optimized. The method validation using Si-GO to extract and concentrate the analytes showed satisfactory results, good sensitivity, good linearity (0.2–4.0 µg L^?1) and low detection limits (1.1–2.9 ng L^?1). The high extraction efficiency was determined with enrichment factors ranging from 1.2–2.9 for the lowest level, 1.3–4.9 intermediate level and 1.2–3.0 highest level (n = 3). Although the analytes were not detected in the real samples evaluated, the method has demonstrated to be efficient through its application in the analysis of spiked triazines in ground and mineral water samples.     

Among- and within-population variation in sperm quality in the simultaneously hermaphroditic land snail Arianta arbustorum

Sperm competition models on the evolution of sperm size assume associations with another sperm quality trait, sperm longevity. Sperm length can also provide an indication of possible mechanisms affecting motility and thus fertilization success. Despite their importance, however, detailed mechanisms of sperm competition at the gamete level are poorly understood. In simultaneously hermaphroditic land snails, sperm traits and cryptic female choice are assumed to be crucial in determining fertilization success. We examined the variation in sperm length and number among individuals from four natural populations of the land snail Arianta arbustorum, a species with multiple mating and long-term sperm storage. We also assessed variation in velocity, motility and longevity of sperm in snails from two of the four populations. Independent of shell size, sperm length differed among populations and, to a minor extent, even among individuals within populations. Mean sperm length of a snail was not correlated with the number of sperm delivered in a spermatophore. The mean sperm velocity (=VCL) did not differ between snails from two populations. However, VCL varied among snails. Percentage motility and longevity of sperm differed between snails from the two populations. No correlations were found between length, velocity, percentage motility and longevity of sperm. To conclude, individual snails differed in sperm quality, and this variation may partly explain the differential fertilization success between A. arbustorum snails. Moreover, our findings did not support the positive association between sperm length and longevity assumed by sperm competition models for internally fertilizing species.     

Cholinesterase characterization and effects of the environmental contaminants chlorpyrifos and carbofuran on two species of marine crabs,Carcinus maenas and Pachygrapsus marmoratus

Among the most frequent targets for toxic effects of modern pesticides, namely organophosphates and carbamates, one may find cholinesterases (ChEs). ChEs exist in a wide variety of animals and have been used actively to discriminate among the environmental effects of different pollutant groups, including the aforementioned pesticides. This study had three purposes, namely (i) identifying the ChE forms present in tissues (eyes and walking legs muscle) of two crab species, Carcinus maenas and Pachygrapsus marmoratus; to (ii) determine the in vitro toxicological effects, and (iii) compare the sensitivity of such enzymatic forms towards commonly used anti-ChE pesticides, namely the organophosphate chlorpyrifos and the carbamate carbofuran. Our results showed that there was not a clear preference for any of the tested substrates in any of the tissues from both species. Furthermore, the ChE activity was almost completely suppressed following incubation with eserine and with the specific inhibitor BW284C51 in all tissues from both species. In vitro exposure to chlorpyrifos promoted a significant decrease in ChE activity in both species. Furthermore, the ChE activity was completely suppressed following incubation with carbofuran and chlorpyrifos. These results suggest that the major ChE forms present in tissues of both crab species show intermediate structural properties and activity patterns, halfway between classic acetylcholinesterase and pseudocholinesterases. However, the sensitivity of the found forms towards ChE inhibitors was established, and the responsiveness of such forms towards common anti-ChE chemicals was established. Both tested species seem to be promising test organisms to be used in marine and coastal scenarios of putative contaminations by anti-ChE chemicals, considering the here reported patterns of response.

     

Phytoremediation of polyaromatic hydrocarbons, anilines and phenols

Phytoremediation technologies based on the combined action of plants and the microbial communities that they support within the rhizosphere hold promise in the remediation of land and waterways contaminated with hydrocarbons but they have not yet been adopted in large-scale remediation strategies. In this review plant and microbial degradative capacities, viewed as a continuum, have been dissected in order to identify where bottle-necks and limitations exist. Phenols, anilines and polyaromatic hydrocarbons (PAHs) were selected as the target classes of molecule for consideration, in part because of their common patterns of distribution, but also because of the urgent need to develop techniques to overcome their toxicity to human health. Depending on the chemical and physical properties of the pollutant, the emerging picture suggests that plants will draw pollutants including PAHs into the plant rhizosphere to varying extents via the transpiration stream. Mycorrhizosphere-bacteria and -fungi may play a crucial role in establishing plants in degraded ecosystems. Within the rhizosphere, microbial degradative activities prevail in order to extract energy and carbon skeletons from the pollutants for microbial cell growth. There has been little systematic analysis of the changing dynamics of pollutant degradation within the rhizosphere; however, the importance of plants in supplying oxygen and nutrients to the rhizosphere via fine roots, and of the beneficial effect of microorganisms on plant root growth is stressed. In addition to their role in supporting rhizospheric degradative activities, plants may possess a limited capacity to transport some of the more mobile pollutants into roots and shoots via fine roots. In those situations where uptake does occur (i.e. only limited microbial activity in the rhizosphere) there is good evidence that the pollutant may be metabolised. However, plant uptake is frequently associated with the inhibition of plant growth and an increasing tendency to oxidant stress. Pollutant tolerance seems to correlate with the ability to deposit large quantities of pollutant metabolites in the 'bound' residue fraction of plant cell walls compared to the vacuole. In this regard, particular attention is paid to the activities of peroxidases, laccases, cytochromes P450, glucosyltransferases and ABC transporters. However, despite the seemingly large diversity of these proteins, direct proof of their participation in the metabolism of industrial aromatic pollutants is surprisingly scarce and little is known about their control in the overall metabolic scheme. Little is known about the bioavailability of bound metabolites; however, there may be a need to prevent their movement into wildlife food chains. In this regard, the application to harvested plants of composting techniques based on the degradative capacity of white-rot fungi merits attention.     

Exposure assessment of operators to pesticides in Kongou,a sub-watershed of Niger River valley

The use of pesticides in horticultural sector in Niger has become an integral part of modern agriculture. Nevertheless, their inappropriate use can generate negative health effects to operators. A study was carried out among Kongou farmers in order to assess their potential dermal exposure (PDE). The UK-POEM model was used to quantify the PDE during mixing/loading and application according to the local practices. In order to determine which parts of the operator body are subject to most contamination during spraying and to validate the theoretical model used, a patch method was used with a tartrazine dye. The deposits of the tartrazine on patches were measured by colorimetry thanks to the absorbance value determined after their extraction in water and a calibration curve. A total of ten spraying trials (five trials with the hand-held sprayer and five others with the backpack sprayer) were performed by different producers at 0.5 and 1 m height for each trial. The survey shows that 92% of the farmers are illiterate and the most common active substances identified are organophosphate or pyrethroids insecticides. Seventy percent of operators do not use any personal protective equipment (PPE) during mixing/loading or spraying. The predictive systemic exposure levels vary from 0.0027?mg kg^?1 bw per day to 0.7692?mg kg^?1 bw per day for backpack sprayer and from 0.0261?mg kg^?1 bw per day to 0.9788?mg kg^?1 bw per day for hand-held sprayer, several times higher the Acceptable Operator Exposure Level (AOEL) for some actives substances. Theoretical modeling indicates more exposure of operator by a hand-held sprayer than a backpack sprayer. The patch method results show that the deposits of dye increase when the position of sprayer nozzle increases from 0.5 to 1 m for the two sprayers. All parts of the operator body are contaminated but lower body parts and chest are the most exposed. The patch method results also show that hand spraying contaminates operator more than backpack spraying, confirming the results of the theoretical model.     

Ultrasound effects on the activity of Aspergillus niger lipases in their application in dairy wastewater treatment

We evaluated the effect of ultrasound radiation on lipase activity. The experiments were conducted using a low‐cost crude enzyme extract. We then used this lipase to treat dairy effluent. The results of our study presented an increase of approximately 430% in the concentration of free fatty acids.     

Minimizing disruptions caused by damming and ensuring the health of downstream ecosystems

In view of the Brazilian Ten‐Year Energy Expansion Plan 2021, this article presents a discussion on environmental flow (e‐flow). The authors analyze the literature to show the evolution of publications concerning e‐flow releases from the perspective of ecosystems services preservation considering results from different case studies from throughout the world. Finally, two main recommendations are drawn regarding e‐flow are: (1) performing a holistic approach to e‐flow planning, including hydrological, hydraulic, water quality, habitat, and riparian zone considerations; and (2) installing in new structures adequate bottom outlets to allow a range of adjustable e‐flow from reservoir dams to reproduce natural flow variations.     

Seasonality and microhabitat selection in a forest-dwelling salamander

Many small terrestrial vertebrates exhibit limited spatial movement and are considerably exposed to changes in local environmental variables. Among such vertebrates, amphibians at present experience a dramatic decline due to their limited resilience to environmental change. Since the local survival and abundance of amphibians is intrinsically related to the availability of shelters, conservation plans need to take microhabitat requirements into account. In order to gain insight into the terrestrial ecology of the spectacled salamander Salamandrina perspicillata and to identify appropriate forest management strategies, we investigated the salamander’s seasonal variability in habitat use of trees as shelters in relation to tree features (size, buttresses, basal holes) and environmental variables in a beech forest in Italy. We used the occupancy approach to assess tree suitability on a non-conventional spatial scale. Our approach provides fine-grained parameters of microhabitat suitability and elucidates many aspects of the salamander’s terrestrial ecology. Occupancy changed with the annual life cycle and was higher in autumn than in spring, when females were found closer to the stream in the study area. Salamanders showed a seasonal pattern regarding the trees they occupied and a clear preference for trees with a larger diameter and more burrows. With respect to forest management, we suggest maintaining a suitable number of trees with a trunk diameter exceeding 30 cm. A practice of selective logging along the banks of streams could help maintain an adequate quantity of the appropriate microhabitat. Furthermore, in areas with a presence of salamanders, a good forest management plan requires leaving an adequate buffer zone around streams, which should be wider in autumn than in spring.