Polyalkylphenyl-sulphonic acids with acid groups of variable strength from animal-vegetable wastes

The insoluble organic fraction isolated from rice-hulls residues and animal fecal matter mixture is sulphonated in liquid SO3 at 200 degrees C to a water soluble sulphonate (III). III is compared to the sulphonate (IV) obtained from the same mix after composting. Both products have been found to contain mixtures of molecules with close molecular weight. These molecules consist of a central cicloaliphatic cluster with peripheral pending aromatic chains. III and IV appear to have the same sulphonation degree. However, the latter contains higher concentrations of cicloaliphatic fragments and of amide, phenol and ether bonds, but less carboxylic and amine functional groups. These differences may be reasonably traced back to the starting materials. By comparison with commercial lignosulphonates derived from the paper and pulp industry, the above arylsulphonates are likely candidates for a variety of applications in the chemical industry and in agriculture. We conclude that sulphonation, even under the drastic experimental conditions of this work, does not seem to erase the memory of the parent matter structure. This reaction is capable of upgrading recalcitrant organic matter in vegetable waste residues to an interesting variety of lignosulphonates.     

Heavy metals monitoring at a Mediterranean natural ecosystem of Central Italy. Trends in different environmental matrixes

The study deals with the evaluation of the impact of heavy metal pollution on a Mediterranean natural ecosystem, and presents the results derived from a monitoring of heavy metals in different environmental matrixes (atmospheric dry depositions, suspended particulate matter (SPM) and stemflow of forest trees). Two sites in Castelporziano Presidential Estate (Rome), one internal and one near the sea-side, were chosen in order to assess the differences in pollutant load. Results showed that heavy metal contamination can arise from local anthropogenic activities, in particular road traffic, and long-range pollution, from industrial and artisan activities near Rome.     

Spray-dry desulfurization of flue gas from heavy oil combustion

An experimental investigation on sulfur dioxide removal in a pilot-scale spray dryer from the flue gas generated by combustion of low-sulfur (S) heavy oil is reported. A limewater slurry was sprayed through an ultrasonic two-fluid atomizer in the spray-dry chamber, and the spent sorbent was collected downstream in a pulse-jet baghouse together with fly ash. Flue gas was sampled at different points to measure the desulfurization efficiency after both the spray-dry chamber and the baghouse. Parametric tests were performed to study the effect of the following variables: gas inlet temperature, difference between gas outlet temperature and adiabatic saturation temperature, lime-to-S ratio, and average size of lime particles in the slurry. Results indicated that spray drying is an effective technology for the desulfurization of low-S fuel oil flue gas, provided operating conditions are chosen carefully. In particular, the lowest gas inlet and outlet temperatures compatible with baghouse operation should be selected, as should a sufficiently high lime-to-S ratio. The attainment of a small lime particle size in the slurry is critical for obtaining a high desulfurization efficiency. A previously presented spray-dry flue gas desulfurization model was used to simulate the pilot-scale desulfurization tests, to check the ability of the model to predict the S capture data and its usefulness as a design tool, minimizing the need for pilot-scale experimentation. Comparison between model and experimental results was fairly good for the whole range of calcium/S ratios considered.     

Lichen biomonitoring of trace metals in the Pistoia area (central northern Italy)

The epiphytic lichen Parmelia caperata (L.) Ach. was used as bioaccumulator of the heavy metals Cd, Cr, Cu, Hg, Ni, Pb and Zn in the environs of the town of Pistoia (central northern Italy). The concentrations of Cd, Cr, Ni, Hg and Pb were comparable with those found in areas not subject to atmospheric pollution. Copper and especially Zn were found in rather high concentrations. Fertilizers and pesticides were the main source of atmospheric contamination.     

Volatile organic compounds produced during the aerobic biological processing of municipal solid waste in a pilot plant

The volatile organic carbon (VOC) and odours emitted during the aerobic biological processing of municipal solid waste (MSW) was studied in a pilot-scale reactor. VOCs were detected by different techniques on solid waste samples and the outlet air stream, before and after a biofilter. Organic compounds (alpha-pinene, beta-myrcene, D-limonene) were also measured in condensate water and leachate from the process. Results showed uniformity in the composition of the air in the solid waste samples, air sampled during the process and condensed water, indicating a matrix-derived origin of these compounds. Leachates, however, contained substances with a quite different molecular structure from the compounds identified in the gaseous fraction. Most of the substances in the gaseous effluent had a hydrocarbon-like structure, mainly terpenoids. The odour produced and detected through olfactometry agreed with GC-MS analyses. This was true above all for terpenes.     

Long-term effect of sewage sludge application on soil humic acids

Sewage sludges are used in agriculture because they act as a fertilizer. Long-term studies are needed to evaluate the effect of sewage sludge on soil properties by paying particular attention to the soil organic matter. Soil plots were amended for 10 years with 1Mg dry matter ha(-1)year(-1) of sewage sludge. Chemical parameters such as total organic carbon (TOC), N, C/N ratio and CEC were determined when this period ended. Moreover, TOC was fractionated into humified and non-humified fractions. Humic acids (HA) were isolated and studied by elemental analysis, DRIFT, (1)H NMR and CPMAS 13C NMR spectroscopies. At the end of the tests, compared to the control soil, the sludge-amended soil did not exhibit change in total organic C and related humified fractions. However, the HA composition of the soil treated with sludge had developed an HA composition closer to that of the HA-sludge as a result of the enrichment of recalcitrant fractions contained in the sludge.     

Use of agro-industrial organic sludge amendment to remediate degraded soil: chemical and eco(geno)toxicological differences between fresh and stabilized sludge and establishment of application rates

Soil degraded by coal mining activities can be remediated by amendment with agro-industrial organic sludge. However, the environmental impacts associated with this management practice must be properly addressed. In this context, the objective of this study was to evaluate the eco(geno)toxicity of a fresh and a stabilized sludge before use in a laboratory soil remediation test. Chemical analysis of the complex mixtures (degraded soil, fresh sludge, and stabilized sludge) was carried out, as well as a battery of eco(geno)toxicity tests on microbiological enzymes (fluorescein hydrolysis), earthworms, and higher plants (including Vicia faba genotoxicity test), according to published methodologies. The results of these tests showed that fresh sludge was more toxic than sludge stabilized over 6 months toward earthworms and higher plants (lettuce, corn, and wild cabbage), while phyto(geno)toxicity tests with V. faba indicated the same genotoxicity levels for the two types of sludge. In the soil remediation simulation using different mixtures of degraded soil and stabilized sludge, the proportions of 50:50 % (dry weight basis) provided the lowest phyto(geno)toxicity effects and this mixture can be used for the revegetation of the contaminated site.     

Food web of a confined and anthropogenically affected coastal basin (the Mar Piccolo of Taranto) revealed by carbon and nitrogen stable isotopes analyses

Carbon and nitrogen stable isotope analysis was used to examine the food web of the Mar Piccolo of Taranto, a coastal basin experiencing several anthropogenic impacts. Main food sources (algal detritus, seaweeds, particulate organic matter (POM) and sediment organic matter (SOM)) and benthic and pelagic consumers were collected during two contrasting seasons (June and April), at four sites distributed over two inlets, and characterized by different level of confinements, anthropogenic inputs and the presence of mussels farming. δ¹³C values of organic sources revealed an important contribution of POM to both planktonic and benthic pathways, as well as the influence of terrigenous inputs within both inlets, probably due to high seasonal land runoff. Although δ¹³C of both sources and consumers varied little between sampling sites and dates, δ¹⁵N spatial variability was higher and clearly reflected the organic enrichment in the second inlet as well as the uptake of anthropogenically derived material by benthic consumers. On the other hand, within the first inlet, the isotopic composition of consumers did not change in response to chemical contamination. However, the impact of polluted sediments near the Navy Arsenal in the first inlet was detectable at the level of the macrobenthic trophic structure, showing high dominance of motile, upper level consumers capable to face transient conditions and the reduction of the more resident deposit feeders. We therefore underline the great potential of matching stable isotope analysis with quantitative studies of community structure to assess the effects of multiple anthropogenic stressors.     

Benthic foraminiferal response to trace element pollution—the case study of the Gulf of Milazzo, NE Sicily (Central Mediterranean Sea)

The response of benthic foraminiferal assemblages to trace element pollution in the marine sediments of the Gulf of Milazzo (north-eastern Sicily) was investigated. Since the 1960s, this coastal area has been a preferred site for the development of two small marinas and a commercial harbour as well as for heavy industry. Forty samples collected in the uppermost 3–4 cm of an undisturbed layer of sediment in the littoral environment were used for this benthic foraminiferal analysis. The enrichment factors (EFs) of selected trace elements (As, Co, Cr, Cu, Mn, Ni, Pb and Zn) were also calculated. Changes both in benthic foraminiferal assemblages and in some trace elements concentrations have provided evidence that the gulf’s littoral zone can be subdivided into three sectors characterised by environmental changes in the marine ecosystem. In the sector unpolluted, close to the Milazzo Cape, foraminiferal assemblages exhibit high values of species richness and foraminiferal density while trace element concentrations and their EFs are very low. Here, the highest densities of Miliolids and epiphytic species are present. On the contrary, in the sector polluted, from the marinas to the crude oil refinery, foraminiferal density and species diversity are low, and assemblages are dominated, albeit with very low densities, by species that tolerate stressed environmental conditions, such as LOFAs, agglutinants and Ammonia spp. Here, the highest trace elements concentrations of Pb, Zn and Cu and related EFs were detected. Eastwards, in the sector moderately polluted, foraminiferal populations are quite poor. They are characterised by low values of species richness and foraminiferal densities, nevertheless trace element concentrations become lower than in the other sectors and their EFs are often below 1. Deformed foraminifera, with percentages up to 7.14 %, were found in all three of the sectors. Differences in benthic foraminiferal assemblages, coupled with results from statistical analysis, indicate that anthropogenic trace element pollution could be considered as one of the most important causes of the modifications of foraminiferal assemblages in the study area.     

Source apportionment and location by selective wind sampling and Positive Matrix Factorization

In order to determine the pollution sources in a suburban area and identify the main direction of their origin, PM_2.5 was collected with samplers coupled with a wind select sensor and then subjected to Positive Matrix Factorization (PMF) analysis. In each sample, soluble ions, organic carbon, elemental carbon, levoglucosan, metals, and Polycyclic Aromatic Hydrocarbons (PAHs) were determined. PMF results identified six main sources affecting the area: natural gas home appliances, motor vehicles, regional transport, biomass combustion, manufacturing activities, and secondary aerosol. The connection of factor temporal trends with other parameters (i.e., temperature, PM_2.5 concentration, and photochemical processes) confirms factor attributions. PMF analysis indicated that the main source of PM_2.5 in the area is secondary aerosol. This should be mainly due to regional contributions, owing to both the secondary nature of the source itself and the higher concentration registered in inland air masses. The motor vehicle emission source contribution is also important. This source likely has a prevalent local origin. The most toxic determined components, i.e., PAHs, Cd, Pb, and Ni, are mainly due to vehicular traffic. Even if this is not the main source in the study area, it is the one of greatest concern. The application of PMF analysis to PM_2.5 collected with this new sampling technique made it possible to obtain more detailed results on the sources affecting the area compared to a classical PMF analysis.