Spatial and statistical assessment of factors influencing nitrate contamination in groundwater

The weights of evidence (WofE) modeling technique has been used to analyze both natural and anthropogenic factors influencing the occurrence of high nitrate concentrations in groundwater resources located in the central part of the Po Plain (Northern Italy). The proposed methodology applied in the Lodi District combines measurements of nitrate concentrations, carried out by means of a monitoring net of 69 wells, with spatial data representing both categorical and numerical variables. These variables describe either potential sources of nitrate and the relative ease with which it may migrate towards groundwater. They include population density, nitrogen fertilizer loading, groundwater recharge, soil protective capacity, vadose zone permeability, groundwater depth, and saturated zone permeability. Once conditional dependence problems among factors have been solved and validation tests performed, the statistical approach has highlighted negative and positive correlations between geoenvironmental factors and nitrate concentration in groundwater. These results have been achieved analysing the calculated statistical parameters (weights, contrasts, normalized contrasts) of each class by which each factor has been previously subdivided. This has permitted to outline: the overall influence each factor has on the presence/absence of nitrate; the range of their values mostly influencing this presence/absence; the most and least critical combination of factor classes existing in each specific zone; areas where the influence of impacting factor classes is reduced by the presence of not impacting factor classes. This last aspect could represent an important support for a correct land use management to preserve groundwater quality.     

Reliability of groundwater vulnerability maps obtained through statistical methods

Statistical methods are widely used in environmental studies to evaluate natural hazards. Within groundwater vulnerability in particular, statistical methods are used to support decisions about environmental planning and management. The production of vulnerability maps obtained by statistical methods can greatly help decision making. One of the key points in all of these studies is the validation of the model outputs, which is performed through the application of various techniques to analyze the quality and reliability of the final results and to evaluate the model having the best performance. In this study, a groundwater vulnerability assessment to nitrate contamination was performed for the shallow aquifer located in the Province of Milan (Italy). The Weights of Evidence modeling technique was used to generate six model outputs, each one with a different number of input predictive factors. Considering that a vulnerability map is meaningful and useful only if it represents the study area through a limited number of classes with different degrees of vulnerability, the spatial agreement of different reclassified maps has been evaluated through the kappa statistics and a series of validation procedures has been proposed and applied to evaluate the reliability of the reclassified maps. Results show that performance is not directly related to the number of input predictor factors and that is possible to identify, among apparently similar maps, those best representing groundwater vulnerability in the study area. Thus, vulnerability maps generated using statistical modeling techniques have to be carefully handled before they are disseminated. Indeed, the results may appear to be excellent and final maps may perform quite well when, in fact, the depicted spatial distribution of vulnerability is greatly different from the actual one. For this reason, it is necessary to carefully evaluate the obtained results using multiple statistical techniques that are capable of providing quantitative insight into the analysis of the results. This evaluation should be done at least to reduce the questionability of the results and so to limit the number of potential choices.     

Analysis of exhausts emitted by i.c. engines and stationary burners, by means of u.v. extinction and fluorescence spectroscopy

Optical investigations of the exhausts emitted by internal combustion (i.c.) engines and a stationary burner were performed, in order to assess their relative role as sources of organic matter to the atmosphere. Extinction spectra of air-diluted exhausts in the 200-400 nm u.v. band reveal the expected existence of gaseous trace-species (NO, NO2 and SO2) and carbonaceous particulate matter (soot). In addition, after subtracting the absorption contribution from known species, a strong residual absorption band remains below 250 nm, which is attributed to organic aromatic matter, involving no more than two aromatic rings. A set of ex situ extinction and laser induced fluorescence (LIF) experiments were carried out on condensed combustion-water samples. Extinction measurements from the water samples show absorption spectra similar to those observed from air-diluted samples, which are attributed to low volatility organic compounds, as they are trapped in the condensed phase. Combining the indications of extinction data for both air-diluted and condensed samples, it is suggested that the absorbing species might be molecular clusters of one/two aromatic rings. LIF spectra from condensed samples evidence two fluorescence bands, centered above 300 and 400 nm, respectively, whose intensities correlate with the combustion regimes. Analogous optical analysis on rain samples, collected in an urban area, showed that rain absorption and fluorescence spectra are similar to those found in condensed exhaust samples, which is consistent with the prevailing contribution of i.c. engines to the urban air pollution. The combined experimental data suggest that the absorbing and fluorescent species trapped in the condensed samples are organic (aromatic) compounds, involving mostly one two aromatic rings structural units, since they do not absorb above 250 nm. The overall molecular weight of the trapped material is likely heavy as they show low volatility.     

Quantifying food losses and the potential for reduction in Switzerland

A key element in making our food systems more efficient is the reduction of food losses across the entire food value chain. Nevertheless, food losses are often neglected. This paper quantifies food losses in Switzerland at the various stages of the food value chain (agricultural production, postharvest handling and trade, processing, food service industry, retail, and households), identifies hotspots and analyses the reasons for losses. Twenty-two food categories are modelled separately in a mass and energy flow analysis, based on data from 31 companies within the food value chain, and from public institutions, associations, and from the literature. The energy balance shows that 48% of the total calories produced (edible crop yields at harvest time and animal products, including slaughter waste) is lost across the whole food value chain. Half of these losses would be avoidable given appropriate mitigation measures. Most avoidable food losses occur at the household, processing, and agricultural production stage of the food value chain. Households are responsible for almost half of the total avoidable losses (in terms of calorific content).     

Monitoring of fuel consumption and aromatics formation in a kerosene spray flame as characterized by fluorescence spectroscopy

The large presence of aromatic compounds in distillate fossil fuels should allow, in line of principle, to follow the fuel consumption and/or the presence of unburned fuel in a high temperature environment like a burner or the exhaust of combustion systems by exploiting the high fluorescence emission of aromatic fuel components. To this aim an UV-excited fluorescence source has to be used since the aromatic fuel components are strongly fluorescing in the UV region of the emission spectrum.

In this work UV-excited laser induced fluorescence (LIF) diagnostics was applied to spray flames of kerosene in order to follow the fuel consumption and the formation of aromatic species. A strong UV signal was detected in the spray region of the flame that presented a shape similar to that found in the LIF spectra preliminary measured on the cold spray and in the room-temperature fluorescence of fuel solutions.

The decrease of UV signal along the spray flame region was associated to the consumption of the fuel, but more difficult seems to be the attribution of a broad visible emission, that is present downstream of the flame.

The visible emission feature could be assigned to flame-formed PAH species contained in the high molecular weight species, hypothesizing that their fluorescence spectra are shifted toward the visible for effect of the high temperature flame environment.     

Slurry wall containment performance: monitoring and modeling of unsaturated and saturated flow

A specific 2-year program to monitor and test both the vadose zone and the saturated zone, coupled with a numerical analysis, was performed to evaluate the overall performance of slurry wall systems for containment of contaminated areas. Despite local physical confinement (slurry walls keyed into an average 2-m-thick aquitard), for at least two decades, high concentrations of chlorinated solvents (up to 110 mg l^− 1) have been observed in aquifers that supply drinking water close to the city of Milan (Italy). Results of monitoring and in situ tests have been used to perform an unsaturated-saturated numerical model. These results yielded the necessary quantitative information to be used both for the determination of the hydraulic properties of the different media in the area and for the calibration and validation of the numerical model. Backfill material in the shallower part of the investigated aquifer dramatically affects the natural recharge of the encapsulated area. A transient simulation from wet to drought periods highlights a change in the ratio between leakages from lateral barriers that support a specific scenario of water loss through the containment system. The combination of monitoring and modelling allows a reliable estimate of the overall performance of the physical confinement to be made without using any invasive techniques on slurry wall.     

Structure of inorganic and carbonaceous particles emitted from heavy oil combustion

The combustion of heavy fuel oil for power generation is a great source of carbonaceous and inorganic particle emissions, even though the combustion technologies and their efficiency are improving. The information about the size distribution function of the particles originated by trace metals present into the fuels is not adequate. In this paper, we focused our attention on the larger distribution mode of both the carbonaceous and metallic particles. Isokinetic sampling was performed at the exhausts of two typical heavy oil flames and the samples were size-segregated by mean of an 8-stages Andersen impactor. Further investigation performed on the samples using electronic microscopy coupled with X-ray analysis (EDX) evidenced the presence of solid spherical particles, called plerosphere(1) as analogy with cenosphere, with typical dimensions ranging between 200 nm and 2-3 microm, whose atomic composition contains a large amount of the trace metals present in the parent oils (Fe, V, Ni, etc). EDX analyses revealed that the metal concentration increases as the plerosphere dimension decreases.