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.     

Flooding in Texas: Examination of Temporal Changes and Impacts of Tropical Cyclones

Annual maximum peak discharge measurements from 62 stations with a record of at least 70 years are used to assess extreme flooding in Texas at the regional scale. This work focuses on examination of the validity of the stationarity assumption and on the impact of tropical cyclones (TCs) on the upper tail of the flood peak distribution. We assess the validity of the stationarity assumption by testing the records for abrupt and gradual changes. The presence of abrupt changes in the first two moments of the flood peak distribution is assessed using the Lombard test. We use the Mann‐Kendall test to examine the presence of monotonic trends. Results indicate that violations of the stationarity assumption are most commonly caused by abrupt changes, which are often associated with river regulation. We fit the time series of stationary flood records with the generalized extreme value distribution to investigate whether TCs control the upper tail of the flood peak distribution. Our results indicate that TCs play a diminished role in shaping the upper tail of the flood peak distribution compared with areas of the eastern United States subject to frequent TCs.     

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.     

Examining Flood Frequency Distributions in the Midwest U.S.1

Villarini, Gabriele, James A. Smith, Mary Lynn Baeck, and Witold F. Krajewski, 2011. Examining Flood Frequency Distributions in the Midwest U.S. Journal of the American Water Resources Association (JAWRA) 47(3):447‐463. DOI: 10.1111/j.1752‐1688.2011.00540.x Abstract: Annual maximum peak discharge time series from 196 stream gage stations with a record of at least 75 years from the Midwest United States is examined to study flood peak distributions from a regional point of view. The focus of this study is to evaluate: (1) “mixtures” of flood peak distributions, (2) upper tail and scaling properties of the flood peak distributions, and (3) presence of temporal nonstationarities in the flood peak records. Warm season convective systems are responsible for some of the largest floods in the area, in particular in Nebraska, Kansas, and Iowa. Spring events associated with snowmelt and rain‐on‐snow are common in the northern part of the study domain. Nonparametric tests are used to investigate the presence of abrupt and slowly varying changes. Change‐points rather than monotonic trends are responsible for most violations of the stationarity assumption. The abrupt changes in flood peaks can be associated with anthropogenic changes, such as changes in land use/land cover, agricultural practice, and construction of dams. The trend analyses do not suggest an increase in the flood peak distribution due to anthropogenic climate change. Examination of the upper tail and scaling properties of the flood peak distributions are examined by means of the location, scale, and shape parameters of the Generalized Extreme Value distribution.     

Translocation of Sb and Ti in an undisturbed floodplain soil after application of Sb2O3 and TiO2 nanoparticles to the surface

The pore water transport of antimony and titanium, applied as nanoparticles (NPs), was studied by spiking stable suspensions of two different nanomaterials on the surface of an undisturbed floodplain soil. For preparation of stable dispersions, two different strategies were followed. (i) Comparable to those used in industrial applications: titanium dioxide nanoparticles, with an average diameter of 99 nm, were prepared by high-energy ball milling in water, whereas for (ii) antimony trioxide (Sb(2)O(3); average diameter 121 nm) a dispersing agent (sodium salt of poly[(naphthaleneformaldehyde)sulfonate] (pNFS) in water) was used. The upper 17 cm of a floodplain soil (river Rhine, Germany) was sampled using the minimally invasive sediment or fauna incubation experiment (SOFIE? two compartment cell; 3 l volume each), which preserved the pore system of the soil. The cells were equipped with 450 and 100 nm filter probes at different depths providing a non-invasive sampling of the pore water. The pore water was sampled at different times (T = 0, 24, 48, 96 and 196 h) and analysed by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS). Sb and Ti were transported via the pore water of the floodplain soil to a depth of 14 cm, corresponding to the maximum cell depth. The highest Sb concentration in the pore water was detected after 24 h at a depth of 5.5-8 cm. Although the spiked concentration was higher for Ti than for Sb, the total Ti concentration in the pore water of the spiked cell was lower. This indicates a stronger agglomeration of TiO(2) NPs or a more intensive interaction of Ti with the solid matrix and a faster transport of Sb towards deeper soil layers. The results show that metal(loid)s from metal oxide NPs are transported in the soil pore water and, hence, have the potential to act as the source of contamination of deeper soil layers after soil surface contamination.     

Are the outputs derived from secondary materials giffen goods?

In this paper we show that under double constraint the goods derived from secondary materials could be Giffen. The example is given of paper derived from waste recycling. We show that if the policy maker misunderstands the type of goods, because he incorrectly considers a Giffen good to be normal, the results of his economic policy could be opposite to his goals. Finally, we make some considerations to generalize our results, and suggest topics for further research.     

False-negative prenatal exclusion of Wiskott-Aldrich syndrome by measurement of fetal platelet count and size

The study of the fetal platelet count and size can, according to the literature, be used for the prenatal diagnosis of the Wiskott-Aldrich syndrome (WAS). So far, no affected fetuses have been identified by this method. All pregnancies in which this method had been applied to resulted, as correctly predicted, in the birth of normal children. Here we report on a familial case of WAS where the haematological parameters failed to reveal the affected second child. Hence we assume that the platelet count and size of platelets remain normal in fetuses with WAS to the gestational age of 22 weeks and cannot be used for prenatal diagnosis.     

Determinants of paternity success in the spider Pholcus phalangioides (Pholcidae: Araneae): the role of male and female mating behaviour

In double mating experiments, we examined whether and to what extent various male and female behavioural traits influence the course of mating and fertilization success in the cellar spider. In males, we focussed on pre-copulatory behaviour and on the rhythmic twisting movements that the male performs with his pedipalps during copulation. In females, we investigated remating decisions and the effect of female termination of copulation. Second males fertilized a high proportion of the eggs (P ₂: median 89%) despite much shorter second matings, with high variation in relative paternity success. The number of pedipalp movements (PPMs) of either male was a better predictor of paternity than copulation duration. Our results suggest that in second matings, PPMs help to remove sperm from previous males, whereas in first matings a high number of PPMs enhances fertilization success, either due to numerical sperm competition or cryptic female choice. Furthermore, we found a negative male age effect on paternity in second matings, implying that age-related deterioration of spermatozoa may promote variation in fertilization success. Female receptivity decreased significantly in second matings; only 70% of the females remated. Females that accepted a second copulation were found to terminate these much earlier and with higher probability than first matings. This suggests that the intensity of conflict between the sexes is higher in second matings. Increased intensity of sexual conflict may be responsible for stronger selection on male traits, as pre-copulatory behaviour and age only affected male copulatory performance and paternity in second matings. Electronic Publication     

Stochastic analysis to assess the spatial distribution of groundwater nitrate concentrations in the Po catchment (Italy)

A large database including temporal trends of physical, ecological and socio-economic data was developed within the EUROCAT project. The aim was to estimate the nutrient fluxes for different socio-economic scenarios at catchment and coastal zone level of the Po catchment (Northern Italy) with reference to the Water Quality Objectives reported in the Water Framework Directive (WFD 2000/60/CE) and also in Italian legislation. Emission data derived from different sources at national, regional and local levels are referred to point and non-point sources. While non-point (diffuse) sources are simply integrated into the nutrient flux model, point sources are irregularly distributed. Intensive farming activity in the Po valley is one of the main Pressure factors Driving groundwater pollution in the catchment, therefore understanding the spatial variability of groundwater nitrate concentrations is a critical issue to be considered in developing a Water Quality Management Plan. In order to use the scattered point source data as input in our biogeochemical and transport models, it was necessary to predict their values and associated uncertainty at unsampled locations. This study reports the spatial distribution and uncertainty of groundwater nitrate concentration at a test site of the Po watershed using a probabilistic approach. Our approach was based on geostatistical sequential Gaussian simulation used to yield a series of stochastic images characterized by equally probable spatial distributions of the nitrate concentration across the area. Post-processing of many simulations allowed the mapping of contaminated and uncontaminated areas and provided a model for the uncertainty in the spatial distribution of nitrate concentrations.     

Biodegradation of petroleum hydrocarbon vapors: laboratory studies on rates and kinetics in unsaturated alluvial sand

Predictions of natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone rely critically on information about microbial biodegradation kinetics. This study aims at determining kinetic rate laws for the aerobic biodegradation of a mixture of 12 volatile petroleum hydrocarbons and methyl tert-butyl ether (MTBE) in unsaturated alluvial sand. Laboratory column and batch experiments were performed at room temperature under aerobic conditions, and a reactive transport model for VOC vapors in soil gas coupled to Monod-type degradation kinetics was used for data interpretation. In the column experiment, an acclimatization of 23 days took place before steady-state diffusive vapor transport through the horizontal column was achieved. Monod kinetic parameters Ks and vmax could be derived from the concentration profiles of toluene, m-xylene, n-octane, and n-hexane, because substrate saturation was approached with these compounds under the experimental conditions. The removal of cyclic alkanes, isooctane, and 1,2,4-trimethylbenzene followed first-order kinetics over the whole concentration range applied. MTBE, n-pentane, and chlorofluorocarbons (CFCs) were not visibly degraded. Batch experiments suggested first-order disappearance rate laws for all VOCs except n-octane, which decreased following zero-order kinetics in live batch experiments. For many compounds including MTBE, disappearance rates in abiotic batch experiments were as high as in live batches indicating sorption. It was concluded that the column approach is preferable for determining biodegradation rate parameters to be used in risk assessment models.