Microbial degradation of 17β -estradiol and 17α -ethinylestradiol followed by a validated HPLC-DAD method

This work aimed at studying the biodegradation of two estrogens, 17α -estradiol (E2) and 17β -ethinylestradiol (EE2), and their potential metabolism to estrone (E1) by microbial consortia. The biodegradation studies were followed by High Performance Liquid Chromatography–Diode Array Detector (HPLC–DAD) using a specifically developed and validated method. Biodegradation studies of the estrogens (E2 and EE2) were carried out with activated sludge (consortium A, CA) obtained from a Wastewater Treatment Plant (WWTP) and with a microbial consortium able to degrade recalcitrant compounds, namely fluorobenzene (consortium B, CB). E2 was more extensively degraded than EE2 by CA whereas CB was only able to degrade E2. The addition of acetate as a supplementary carbon source led to a faster biodegradation of E2 and EE2. E1 was detected as a metabolite only during the degradation of E2. The 16S rRNA gene sequence analyses of strains recovered from the degrading cultures revealed the presence of the genera Pseudomonas, Chryseobacterium and Alcaligenes. The genera Pseudomonas and Chryseobacterium were retrieved from cultures supplied with E2 and EE2, while the genus Alcaligenes was found in the presence of E2, suggesting that they might be involved in the degradation of these compounds.     

Microstructure of the paper nautilus (Argonauta nodosa) shell and the novel application of electron backscatter diffraction (EBSD) to address effects of ocean acidification

Electron backscatter diffraction (EBSD) is a powerful microscopic technique to characterise the crystallography of biomineralisation. Here, we use high-resolution EBSD to characterise one of the least studied shells in the ocean, the female argonaut brood chamber, and to examine the changes in shell microstructure in response to incubation in decreased pH conditions. The thin (225 μm) shell of Argonauta nodosa is magnesium calcite with an average magnesium content of ca. 5.1 Wt % MgCO₃. EBSD and scanning electron microscopy (SEM) revealed that calcification of the shell is bidirectional with formation of irregular crystalline grains. Following a 2 week incubation in a range of pH treatments (pH, 8.1–7.2), shell fragment weight decreased by dissolution in pH ≤ 7.8. EBSD and SEM revealed altered shell crystallography and microstructure at pH ≤ 7.4 due to preferential etching down crystallite grain boundaries and a change in crystalline orientation on both the inner and outer shell surfaces. Our study highlights the value of EBSD for the detailed examination of biogenic carbonates and its potential use in the field of ocean acidification research.     

Soil Zinc contamination from corrosion of galvanized structures

The present work relates to galvanized structures with several years of time life subjected to atmospheric corrosion, like galvanized high tension steel pylons. The mass and fate of zinc released is evaluated both via empirical and experimental procedures. The corrosion rate determination requested atmospheric condition characterization, especially for SO 2 concentration and experimental activities focused on soil sampling around pylons. The soil zinc content, total and exchangeable, is determinates by different analytical procedures. The zinc diffusion in environment and the zinc extension under the top soil is evaluated using 1-dimensional mathematical model for miscible species in porous soil.     

Evaluation of the impact on entomocoenosis of active agents allowed in organic olive farming against Bactrocera oleae (Gmelin, 1790)

Several attempts for evaluating environmental impact of active agents allowed in organic olive farming against Bactrocera oleae have been made, but very few studies were performed contemporaneously on more than one of them. Insects were chosen as indicators because they are known to react very quickly to environmental perturbations, mainly at the community level. In fact, the coenosis is the functional unit interacting with biotic and abiotic environmental parameters. Seven taxa, known for their sensitivity to habitat alterations, were sampled and grouped in functional groups: predators and parasitoids, phytophagouses and pollinators. The coenotic balance between these two functional groups was analyzed. The study was carried out in an organic olive orchard in the municipality of Terranova da Sibari, Cosenza, Southern Italy. The tested active agents (Azadirachtin, Rotenone, Copper Oxychloride) were sprayed twice (end of September and middle October). During the treatments the population dynamics of all the taxa were knocked-down. No one tested compound seems to be harmless to the entomocoenosis, particularly on phytophagouses and pollinators. In truly organic farming it is necessary to provide natural refuge areas to beneficial insects (i.e. pest antagonists) in which no active agents are sprayed and alternative preys could be found.     

Effect of impeller type and agitation on the performance of pilot scale ASBR and AnSBBR applied to sanitary wastewater treatment

The objective of this work was to assess the effect of agitation rate and impeller type in two mechanically stirred sequencing batch reactors: one containing granulated biomass (denominated ASBR) and the other immobilized biomass on polyurethane foam (denominated AnSBBR). Each configuration, with total volume of 1 m³, treated 0.65 m³ sanitary wastewater at ambient temperature in 8-h cycles. Three impeller types were assessed for each reactor configuration: flat-blade turbine impeller, 45°-inclined-blade turbine impeller and helix impeller, as well as two agitation rates: 40 and 80 rpm, resulting in a combination of six experimental conditions. In addition, the ASBR was also operated at 20 rpm with a flat-blade turbine impeller and the AnSBBR was operated with a draft tube and helix impeller at 80 and 120 rpm. To quantify how impeller type and agitation rate relate to substrate consumption rate, results obtained during monitoring at the end of the cycle, as well as the time profiles during a cycle were analyzed. Increasing agitation rate from 40 rpm to 80 rpm in the AnSBBR improved substrate consumption rate whereas in the ASBR this increase destabilized the system, likely due to granule rupture caused by the higher agitation. The AnSBBR showed highest solids and substrate removal, highest kinetic constant and highest alkalinity production when using a helix impeller, 80 rpm, and no draft tube. The best condition for the ASBR was achieved with a flat-blade turbine impeller at 20 rpm. The presence of the draft tube in the AnSBBR did not show significant improvement in reactor efficiency. Furthermore, power consumption studies in these pilot scale reactors showed that power transfer required to improve mass transfer might be technically and economically feasible.     

Validation of a multiclass multiresidue method and monitoring results for 210 pesticides in fruits and vegetables by gas chromatography-triple quadrupole mass spectrometry

A rapid, sensitive, accurate and reliable multiresidue method for the identification and quantification of 210 relevant pesticides in four representative fruit and vegetable commodities (tomato, potato, spring onion and orange) has been developed and validated by gas chromatography in tandem with triple quadrupole mass spectrometry. The method has been fully validated and applied to 292 samples from different countries. Prior to instrumental analysis, an extraction procedure based on a sample extraction of multiclass analytes, using the ethyl acetate method was employed. Mass spectrometric conditions were individually optimized for each compound in the selected reaction monitoring (SRM) mode to achieve maximum sensitivity. The pesticides were separated in less than 25 min. This was followed by an exhaustive control of the retention times. The Retention Time Locking Method was applied, working at a constant pressure throughout the analysis. System maintenance was reduced by using a purged capillary flow device that provided backflush capabilities by reversing column flow immediately after elution of the last compound of interest. Istotopically labelled internal standards were employed to improve the quality of the analytical results.     

Metal extractability patterns to evaluate (potentially) mobile fractions in periurban calcareous agricultural soils in the Mediterranean area—analytical and mineralogical approaches

A set of periurban calcareous agricultural Mediterranean soils was spiked with a mixture of Cd, Cu, Pb and Zn at two levels within the limit values proposed by current European legislation, incubated for up to 12 months, and subjected to various one-step extraction procedures to estimate mobile (neutral salts) and potentially mobile metal fractions (complexing and acidic extraction methods). The results obtained were used to study metal extractability patterns according to the soil characteristics. The analytical data were coupled with mineralogical investigations and speciation modelling using the Visual Minteq model. The formation of soluble metal-complexes in the complexing extracts (predicted by the Visual Minteq calculations) led to the highest extraction efficiency with complexing extractants. Metal extractability patterns were related to both content and composition of carbonate, organic matter, Fe oxide and clay fractions. Potentially mobile metal fractions were mainly affected by the finest soil fractions (recalcitrant organic matter, active lime and clay minerals). In the case of Pb, scarce correlations between extractable Pb and soil constituents were obtained which was attributed to high Pb retention due to the formation of 4PbCO₃·3PbO (corroborated by X-ray diffraction). In summary, the high metal proportion extracted with complexing agents highlighted the high but finite capacity to store potentially mobilizable metals and the possible vulnerability of these soils against environmental impact from metal accumulation.     

Perfluoroalkyl substances (PFASs) in food and water from Faroe Islands

Diet and drinking water are suggested to be major exposure pathways for perfluoroalkyl substances (PFASs). In this study, food items and water from Faroe Islands sampled in 2011/2012 were analyzed for 11 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkane sulfonic acids (PFSAs). The food samples included milk, yoghurt, crème fraiche, potatoes, fish, and fish feed, and the water samples included surface water and purified drinking water. In total, nine PFCAs and four PFSAs were detected. Generally, the levels of PFAS were in the lower picogram per gram range. Perfluorobutanoic acid was a major contributor to the total PFASs concentration in water samples and had a mean concentration of 750 pg/L. Perfluoroundecanoic acid (PFUnDA) was predominating in milk and wild fish with mean concentrations of 170 pg/g. Perfluorooctane sulfonic acid (PFOS) was most frequently detected in food items followed by PFUnDA, perfluorononanoic acid, and perfluorooctanoic acid (PFOA). Levels of PFUnDA and PFOA exceeded those of PFOS in milk and fish samples. Prevalence of long-chain PFCAs in Faroese food items and water is confirming earlier observations of their increase in Arctic biota. Predominance of short-chain and long-chain homologues indicates exposure from PFOS and PFOA replacement compounds.