Phototransformation of <Emphasis Type="SmallCaps">l</Emphasis>-tryptophan and formation of humic substances in water

Humic substances are poorly known, though they represent a major pool of non-biotic organic carbon on earth. In particular, there is little knowledge on the formation of humic substances by irradiation of organic matter dissolved in waters. Specifically, it is known that humic substances can be formed from proteins by photochemical processes in surface waters, but the role of single amino acids and their transformation pathways are not yet known. Therefore, here we studied the phototransformation of aqueous l-tryptophan under simulated sunlight. Irradiated l-tryptophan solutions were analyzed by absorption, fluorescence, nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies, chromatography, potentiometry and mass spectrometry (MS). The solutions appeared turbid after irradiation; therefore, nephelometry and dynamic laser light scattering were used to characterize the suspended particles. Results show that about 95% of l-tryptophan was degraded in 8-h irradiation, undergoing deamination and decarboxylation of the amino acidic moieties to release ammonium and formate. The MS signal at m/z 146 suggests the formation of 3-ethylindole, while pH-metric and NMR data revealed the presence of hydroxylated compounds. The phototransformation intermediates of l-tryptophan had fluorescence and absorption spectra similar to those of humic substances, they were able to produce ^·OH upon irradiation and tended to aggregate by both ionic and hydrophobic interactions. Overall, our findings reveal for the first time the nature of products formed upon phototransformation of l-tryptophan. Interestingly, the transformation of l-tryptophan is quite different from that of the previously studied l-tyrosine, although both compounds produce humic-like materials under irradiation.     

Nitrogen Budget in a Lowland Coastal Area Within the Po River Basin (Northern Italy): Multiple Evidences of Equilibrium Between Sources and Internal Sinks

Detailed studies on pollutants genesis, path and transformation are needed in agricultural catchments facing coastal areas. Here, loss of nutrients should be minimized in order to protect valuable aquatic ecosystems from eutrophication phenomena. A soil system N budget was calculated for a lowland coastal area, the Po di Volano basin (Po River Delta, Northern Italy), characterized by extremely flat topography and fine soil texture and bordering a network of lagoon ecosystems. Main features of this area are the scarce relevance of livestock farming, the intense agriculture, mainly sustained by chemical fertilizers, and the developed network of artificial canals with long water residence time. Average nitrogen input exceeds output terms by ~60 kg N ha^?1 year^?1, a relatively small amount if compared to sub-basins of the same hydrological system. Analysis of dissolved inorganic nitrogen in groundwater suggests limited vertical loss and no accumulation of this element, while a nitrogen mass balance in surface waters indicates a net and significant removal within the watershed. Our data provide multiple evidences of efficient control of the nitrogen excess in this geographical area and we speculate that denitrification in soil and in the secondary drainage system performs this ecosystemic function. Additionally, the significant difference between nitrogen input and nitrogen output loads associated to the irrigation system, which is fed by the N-rich Po River, suggests that this basin metabolizes part of the nitrogen excess produced upstream. The traditionally absent livestock farming practices and consequent low use of manure as fertilizer pose the risk of excess soil mineralization and progressive loss of denitrification capacity in this area.     

Size and spatial structure in deep versus shallow populations of the Mediterranean gorgonian <Emphasis Type="Italic">Eunicella singularis</Emphasis> (Cap de Creus,northwestern Mediterranean Sea)

In the Western Mediterranean Sea, the gorgonian Eunicella singularis (Esper, 1794) is found at high densities on sublittoral bottoms at depths from 10 to 70 m. Shallow colonies have symbiotic zooxanthellae that deeper colonies lack. While knowledge of the ecology of the shallow populations has increased during the last decades, there is almost no information on the ecology of the deep sublittoral populations. In October and November 2004 at Cap de Creus (42°19′12″ N; 03°19′34″ E), an analysis of video transects made by a remotely operated vehicle showed that shallow populations (10–25 m depth) were dominated by small, non-reproductive colonies, while deep sublittoral populations (50–67 m depth) were dominated by medium-sized colonies. Average and maximum colony heights were greater in the deeper populations, with these deeper populations also forming larger patch sizes and more extensive regions of continuous substrate coverage. These results suggest that shallow habitats are suitable for E. singularis, as shown by the high recruitment rate, but perturbations may limit or delay the development of these populations into a mature stage. This contrasts with the deep sublittoral habitats where higher environmental stability may allow the development of mature populations dominated by larger, sexually mature colonies.     

Rapid analysis of neonicotinoid insecticides in guttation drops of corn seedlings obtained from coated seeds

Regarding the hypothesis that neonicotinoid insecticides used for seed coating of agricultural crops - mainly corn, sunflower and seed rape - are related to the extensive death of honey bees, the phenomenon of corn seedling guttation has been recently considered as a possible route of exposure of bees to these systemic insecticides. In the present study, guttation drops of corn plants obtained from commercial seeds coated with thiamethoxam, clothianidin, imidacloprid and fipronil have been analyzed by an optimized fast UHPLC-DAD procedure showing excellent detection limits and accuracy, both adequate for the purpose. The young plants grown both in pots - in greenhouse - and in open field from coated seeds, produced guttation solutions containing high levels of the neonicotinoid insecticides (up to 346 mg L(-1) for imidacloprid, 102 mg L(-1) for clothianidin and 146 mg L(-1) for thiamethoxam). These concentration levels may represent lethal doses for bees that use guttation drops as a source of water. The neonicotinoid concentrations in guttation drops progressively decrease during the first 10-15 days after the emergence of the plant from the soil. Otherwise fipronil, which is a non-systemic phenylpyrazole insecticide, was never detected into guttation drops. Current results confirm that the physiological fluids of the corn plant can effectively transfer neonicotinoid insecticides from the seed onto the surface of the leaves, where guttation drops may expose bees and other insects to elevated doses of neurotoxic insecticides.     

Database-driven models of the world's Large Marine Ecosystems

We present a new methodology for database-driven ecosystem model generation and apply the methodology to the world's 66 currently defined Large Marine Ecosystems. The method relies on a large number of spatial and temporal databases, including FishBase, SeaLifeBase, as well as several other databases developed notably as part of the Sea Around Us project. The models are formulated using the freely available Ecopath with Ecosim (EwE) modeling approach and software. We tune the models by fitting to available time series data, but recognize that the models represent only a first-generation of database-driven ecosystem models. We use the models to obtain a first estimate of fish biomass in the world's LMEs. The biggest hurdles at present to further model development and validation are insufficient time series trend information, and data on spatial fishing effort.     

Protecting the photosynthetic performance of snap bean under free air ozone exposure

Tropospheric ozone(O_3) is a major air pollutant and causes serious injury to vegetation. To protect sensitive plants from O_3 damage, several agrochemicals have been assessed,including cytokinin(e.g., kinetin, KIN) and ethylenediurea(EDU) with cytokinin-like activity.In higher plant, leaves are primarily injured by O_3 and protective agrochemicals are often applied by leaf spraying. To our knowledge, the mitigating abilities of EDU and KIN have not been compared directly in a realistic setup. In the present research, impacts of elevated O3(2 × ambient O_3, 24 hr per day, for 8 days) on an O_3 sensitive line(S156) of snap bean(Phaseolus vulgaris), which is often used for biomonitoring O_3 pollution, were studied in a free air controlled exposure system. The day before starting the O_3 exposure, plants were sprayed with a solution of EDU(300 ppm), KIN(1 mmol/L) or distilled water, to compare their protective abilities. The results demonstrated that 2 × ambient O_3 inhibited net photosynthetic rate and stomatal conductance, increased the minimal fluorescence yield of the dark-adapted state, decreased the maximal quantum yield of PSII photochemistry, and led to visible injury. KIN and EDU alleviated the reduction of the photosynthetic performance, and visible injury under O_3 fumigation. The plants sprayed with EDU showed greater ability to mitigate the O_3 damage than those sprayed with KIN. Chlorophyll fluorescence imaging may have detected more precisely the differences in O_3 response across the leaf than the conventional fluorometer.     

Determination of particulate polycyclic aromatic hydrocarbons in ambient air by gas chromatography-mass spectrometry after molecularly imprinted polymer extraction

A solid phase extraction procedure (SPE) is described for the quantitative analysis of polycyclic aromatic hydrocarbons (PAHs) in atmospheric particulate matter (PM), as ubiquitous environmental pollutants routinely measured in air quality monitoring. A SPE cartridge was used based on a molecular imprinted polymer (MIP-SPE) properly tailored for selective retention of PAHs with 4 and more benzene fused rings. The performance of the clean-up procedure was evaluated with the specific concern of selective purification towards saturated hydrocarbons, which are the PM components mostly interfering GC analysis of target PAHs. Under optimized operative conditions, the MIP-SPE provided analyte recovery close to 95% for heavier PAHs, from benzo(α)pyrene to benzo(ghi)perylene, and close to 90% for four benzene rings PAHs, with good reproducibility (RSDs: 2.5%-5.9%). Otherwise, C₁₇-C₃₂ n-alkanes were nearly completely removed. The proposed method was critically compared with Solid Phase Micro Extraction (SPME) using a polyacrylate fiber. Both methods were successfully applied to the analysis of ambient PM_2.5 samples collected at an urban polluted site. Between the two procedures, the MIP-SPE provided the highest recovery (R% ≥ 93%) for PAHs with 5 and more benzene rings, but lower for lighter PAHs. In contrast, SPME showed a mean acceptable R% value (∼ 80%) for all the investigated PAHs, except for the heaviest PAHs in the most polluted samples (R%: 110%-138%), suggesting an incomplete purification from the interfering n-hydrocarbons.     

Computation of the interfacial area for two-fluid porous medium systems

We develop a method to compute interfacial areas from three-dimensional digital representations of multiphase systems. We approximate the interfaces with the isosurface generated by the standard marching-cube algorithm from the discrete phase distribution. We apply this approach to two-fluid pore-scale simulations by (1) simulating a random packing of spheres that obeys the grain-size distribution and porosity of an experimental porous medium system, and (2) using a previously developed pore-morphology-based model in order to predict the phase distribution for a water-wet porous medium that undergoes primary drainage. The predicted primary drainage curve and interfacial areas are in good agreement with the experimental values reported in the literature, where interfacial areas were measured using interfacial tracers. The energy dissipation during Haines jumps is significant: thus, the mechanical work done on the system is not completely converted into surface energy, and interfacial areas may not be deduced from the primary drainage curve.     

Evaluation of mercury biogeochemical cycling at the sediment–water interface in anthropogenically modified lagoon environments

The Marano and Grado Lagoon is well known for being contaminated by mercury(Hg) from the Idrija mine(Slovenia) and the decommissioned chlor-alkali plant of Torviscosa(Italy).Experimental activities were conducted in a local fish farm to understand Hg cycling at the sediment–water interface. Both diffusive and benthic fluxes were estimated in terms of chemical and physical features. Mercury concentration in sediments(up to 6.81 μg/g)showed a slight variability with depth, whereas the highest methylmercury(MeHg) values(up to 10 ng/g) were detected in the first centimetres. MeHg seems to be produced and stored in the 2–3 cm below the sediment–water interface, where sulphate reducing bacteria activity occurs and hypoxic–anoxic conditions become persistent for days. DMeHg in porewaters varied seasonally(from 0.1 and 17% of dissolved Hg(DHg)) with the highest concentrations in summer. DHg diffusive effluxes higher(up to 444 ng/m~2/day) than those reported in the open lagoon(~ 95 ng/m~2/day), whereas DMeHg showed influxes in the fish farm(up to-156 ng/m~2/day). The diurnal DHg and DMeHg benthic fluxes were found to be higher than the highest summer values previously reported for the natural lagoon environment. Bottom sediments, especially in anoxic conditions, seem to be a significant source of MeHg in the water column where it eventually accumulates. However, net fluxes considering the daily trend of DHg and DMeHg, indicated possible DMeHg degradation processes. Enhancing water dynamics in the fish farm could mitigate environmental conditions suitable for Hg methylation.