Effect of water composition on the photocatalytic removal of pesticides with different TiO2 catalysts

The objective of this work is double—firstly to explore the photocatalytic efficiency of five different commercial TiO₂ catalysts in the photodegradation of a mixture of pesticides classified by the EU as priority pollutants and secondly to analyze the correlation between their physicochemical properties and the inhibition of the studied photocatalytic process when natural water was employed. Photocatalytic efficiencies when ultrapure water was used seem to point out that surface area was not a prerequisite for the photodegradation of the selected mixture of pesticides. On the other hand, significant differences in total organic carbon (TOC) conversions were obtained with the two studied water compositions. On one side, Evonik materials appear to be mostly inhibited when natural water was employed, whereas on the other, it should be remarked that anatase Sigma-Aldrich (SA) and, particularly, Hombikat UV100 (HBK) materials presented a very limited photo-efficiency inhibition or even a higher initial rate of TOC removal when a natural water matrix was used, probably due to their specific surface properties (PZC, S _BET). Therefore, heterogeneous photocatalysis has proved to be a promising technology for the degradation of the selected mixture of pesticides where the final photo-efficiency of the five commercial titania catalysts studied here responds to a complex balance between its surface and structural properties.     

‘End to end’ planktonic trophic web and its implications for the mussel farms in the Mar Piccolo of Taranto (Ionian Sea,Italy)

The Mar Piccolo is a semi-enclosed basin subject to different natural and anthropogenic stressors. In order to better understand plankton dynamics and preferential carbon pathways within the planktonic trophic web, an integrated approach was adopted for the first time by examining all trophic levels (virioplankton, the heterotrophic and phototrophic fractions of pico-, nano- and microplankton, as well as mesozooplankton). Plankton abundance and biomass were investigated during four surveys in the period 2013–2014. Beside unveiling the dynamics of different plankton groups in the Mar Piccolo, the study revealed that high portion of the plankton carbon (C) pool was constituted by small-sized (<2 μm) planktonic fractions. The prevalence of small-sized species within micro- and mesozooplankton communities was observed as well. The succession of planktonic communities was clearly driven by the seasonality, i.e. by the nutrient availability and physical features of the water column. Our hypothesis is that beside the ‘bottom-up’ control and the grazing pressure, inferred from the C pools of different plankton groups, the presence of mussel farms in the Mar Piccolo exerts a profound impact on plankton communities, not only due to the important sequestration of the plankton biomass but also by strongly influencing its structure.     

The size distribution of organic carbon in headwater streams in the Amazon basin

Despite the strong representativeness of streams in the Amazon basin, their role in the accumulation of coarse particulate organic carbon (CPOC), fine particulate organic carbon (FPOC), and dissolved organic carbon (DOC) in transport, an important energy source in these environments, is poorly known. It is known that the arboreal vegetation in the Amazon basin is influenced by soil fertility and rainfall gradients, but would these gradients promote local differences in organic matter in headwater streams? To answer this question, 14 low-order streams were selected within these gradients along the Amazon basin, with extensions that varied between 4 and 8 km. The efficiency of the transformation of particulate into dissolved carbon fractions was assessed for each stream. The mean monthly benthic organic matter storage ranged between 1.58 and 9.40 t ha^?1 month^?1. In all locations, CPOC was the most abundant fraction in biomass, followed by FPOC and DOC. Rainfall and soil fertility influenced the distribution of the C fraction (p?=?0.01), showing differentiated particulate organic carbon (POC) storage and DOC transportation along the basin. Furthermore, the results revealed that carbon quantification at the basin level could be underestimated, ultimately influencing the global carbon calculations for the region. This is especially due to the fact that the majority of studies consider only fine particulate organic matter and dissolved organic matter, which represent less than 50 % of the stored and transported carbon in streambeds.     

PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism

In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by transmission electron microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products.     

Environmental information sharing: a means to support the legitimization of oyster farmers’ stewardship over water quality management in NSW,Australia

Oyster farmers depend on good water quality. Activities upstream from estuaries result in externalities that impact water quality. Over the last 10 years, oyster farmers have been developing estuary‐wide environmental management systems ( EMSs ) to tackle internal (i.e. industry‐related) and external (i.e. catchment) issues in N ew S outh W ales, A ustralia. Drawing on interview‐based research and document analyses, this paper shows that the process of creating an EMS for the oyster industry, as well as the creation of the EMS itself, resulted in legitimizing the industry's stewardship over the natural resource it depends on (water). For the oyster industry, this result was due to a change in the scale on which EMSs have been developed: instead of viewing issues at the individual business level, the systems expanded their viewpoint to the entire catchment, and included every oyster business in the estuary, as well as all other activities in the upper catchment. By providing a means of communicating internal efforts and with the support of local government bodies, EMSs provided a mechanism with which influence over upstream actors and activities could be exerted. We demonstrate this by using the ‘social‐ecological systems’ and ‘ ENCORE ’ frameworks, emphasizing the transitions that allowed for this change of scale to take place.     

Metallophyte status of violets of the section Melanium

Violets from metal-enriched soils have controversially been described as both heavy-metal accumulators and excluders in the literature. The present study solves the issue for violets of the section Melanium (zinc violets, Viola lutea ssp. calaminaria and V. lutea ssp. westfalica; hartsease or wild pansy, Viola tricolor; and mountain pansy, V. lutea). The aims were to determine the concentrations of heavy metals in the soil and in the roots and shoots of field-collected plants, to evaluate the potential impact of colonisation by arbuscular mycorrhizal fungi on heavy-metal concentrations in the plant tissues, and to quantitatively define the localisation of the elements in root cross-sections. When these violets grow in low-metal soils, higher concentrations of the heavy metals were found in the roots and shoots than in the soil, whereas the opposite was seen in samples from high-metal soils. Under all field conditions examined, the roots of all of these species were colonised by arbuscular mycorrhizal fungi. However, V. tricolor was marginally colonised when the concentrations of Zn and P were higher in the soil. Determination of the spatial distribution of the elements in root cross-sections of these violets indicates tissue-specific deposition of elements within the vascular tissue, the cortex, and the rhizodermis. These data indicate that violets of the section Melanium are heavy-metal excluders.     

Microalgae biosynthesis of silver nanoparticles for application in the control of agricultural pathogens

The occurrence of diseases in cultivars has caused significant losses in global food production. The advancement of nanobiotechnology makes it possible to obtain new products to be used in the control of pathogens in cultivars. Silver nanoparticles can be synthesized by microalgae and are widely known for their antimicrobial activity. In addition, the biomass produced in microalgal culture for the biosynthesis of the nanoparticles also demonstrates antimicrobial properties, as it can increase the antibacterial and antifungal potential of the silver nanoparticles. In this context, this article addresses the use of microalgae to biosynthesize silver nanoparticles simultaneously with biomass production. In addition, we demonstrate the antimicrobial potential of these nanomaterials, as well as of the microalgal biomass produced in biosynthesis, to use in the control of pathogens in agriculture.     

Evaluation of a multiresidue method for pesticides in cereals using supercritical fluid extraction and gas chromatographic detection

Supercritical fluid extraction (SFE) was evaluated to be applied for residue analysis of 22 gas chromatography/electron capture detector-nitrogen phosphorus detector (GC/ECD-NPD) amenable pesticides in rice, wild rice and wheat. Samples were extracted with supercritical carbon dioxide at 200 atm pressure and 50°C temperature, using methanol as a static modifier. Mean recoveries obtained with the proposed SFE method at two spiking levels with four replicates per level are compared with those obtained with an ethyl acetate-based solvent extraction/gel permeation chromatography (GPC) clean up method. Both methods gave consistent high recoveries for almost all the pesticides from all the commodities with overall mean recoveries higher than 70% with relative standard deviations lower than 20%. Remarkable exceptions were captafol and dimethoate, for which low and/or non-reproducible recoveries were obtained with the SFE method. Residue levels determined with both methods in nine different incurred samples of wheat, containing some of the studied pesticides, were very similar, but, in all cases, slightly higher levels were determined with the SFE method.     

Sorption and photodegradation of chlorpyrifos on riparian and aquatic macrophytes

Surface water bodies may become contaminated via spray drift following pesticide application. In this investigation, the photodegradation and sorption of chlorpyrifos was studied in four riparian macrophytes representative of Mediterranean flora (Phragmites australis, Iris pseudacorus, Equisetum pratense and Typha latifolia). The results of experiments with both the active ingredient and the formulation DURSBAN 48® EC confirm the ability of these species to interact with chemicals such as chlorpyrifos. The maximum sorption of chlorpyrifos at equilibrium was observed in Phragmites australis (22%). And, the maximum instantaneous sorption of chlorpyrifos was observed in the dried biomass of Phragmites australis (49%). The epicuticular waxes present on leaves influence photodegradation processes, resulting in a decrease in chlorpyrifos persistence depending on the nature of the extract. The half-life of chlorpyrifos residues in leaf waxes decreased from 34 to 99 minutes when irradiated.