Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

Dental enamel as biomarker for environmental contaminants in relevant industrialized estuary areas in São Paulo,Brazil

Heavy metal contamination is a long-standing and very well-known public health problem, and its exposure can cause damage to several organs of human body, especially on the central nervous system of young children and teenagers. The aim of this article is to evaluate lead, cadmium, and manganese contamination in 125 children from 6 to 13 years old living in contaminated areas during the period from 2006 to 2009 (São Vicente, Cubatão Downtown, Bertioga and Cubatão Pilões/Água Fria). This estuary area is the most important example of environmental degradation by chemicals from industrial sources. This is a cross-sectional study through clinical examinations and dental enamel tests. All mothers from these children lived in the area since before the pregnancy. Lead, cadmium, and manganese levels (μg/g) were measured on dental enamel samples through graphite furnace atomic absorption spectrometry, searching for the occurrence of heavy metals. The mean lead concentrations were 139.48 μg/g in Cubatão Pilões/Água Fria, 170.45 μg/g in Cubatão Downtown, 213.52 μg/g in São Vicente, and 151.89 μg/g in Bertioga. The mean cadmium concentrations were 10.83 μg/g in Cubatão Pilões/Água Fria, 12.58 μg/g in Cubatão Downtown, 10.92 μg/g in São Vicente, and 14.57 μg/g in Bertioga. The mean manganese concentrations were 23.49 μg/g in Cubatão Pilões/Água Fria, 30.90 μg/g in Cubatão Downtown, 41.46 μg/g in São Vicente, and 42.00 μg/g in Bertioga. Dental surface enamel may be used as an efficient biomarker of past environmental exposure to lead, manganese, and cadmium which are associated to well-known sources of heavy metal contamination. The results suggest that the evaluated children were exposed to sources of lead, cadmium, and manganese since before their conceptions. Although Bertioga initially was chosen as a control area of this study, it was also was verified to have heavy metal contamination on examined children.     

Integrated hydrologic–economic decision support system for groundwater use confronting climate change uncertainties in the Tunuyán River basin,Argentina

This study presents an integrated hydrologic–economic model as decision support system for groundwater use and incorporates uncertainties of climate change. The model was developed with the Vensim software (Ventana Systems) for system dynamic simulations. The software permitted the integration of economic variables along with hydrologic variables, in a unified format with the aim of evaluating the economic impacts of climate change on arid environments. To test the model, we applied it in one of the upper Tunuyán River sub-basin, located in the Mendoza Province (Argentina), where irrigation comes from groundwater. The model defines the best mix of crops and the total land use required to maximize the total river sub-basin monetary income, considering as a limit the amount of water that does not exceed the natural annual aquifer recharge. To estimate the impacts of climatic changes, four scenarios were compared: the business as usual (with the number of existing wells) in a dry year with a temperature increase of 4 °C; the business as usual in a wet year with an increase in temperature of 1.1 °C; an efficient use of wells in a dry year and a temperature increase of 4 °C and an efficient use of wells in a wet year with a temperature increase of 1.1 °C. Outputs calculated by the model were: land use per crop, total sub-basin net benefit, total sub-basin water extraction, water extraction limit depending on river discharge and total number of wells required to irrigate the entire area. Preliminary results showed that the number of existing wells exceeded the optimized number of wells required to sustainably irrigate the entire river sub-basin. Results indicated that in an average river discharge year, if wells were efficiently used, further rural development would be possible, until the limit of 350 million m³ of water extraction per year was reached (650 million m³ for a wet year and 180 million m³ for a dry year). The unified format and the low cost of the software license make the model a useful tool for Water Resources Management Institutions, particularly in developing countries.     

Biodegradation of aromatic hydrocarbons by Haloarchaea and their use for the reduction of the chemical oxygen demand of hypersaline petroleum produced water

Ten halophilic Archaea (Haloarchaea) strains able to degrade aromatic compounds were isolated from five hypersaline locations; salt marshes in the Uyuni salt flats in Bolivia, crystallizer ponds in Chile and Cabo Rojo (Puerto Rico), and sabkhas (salt flats) in the Persian Gulf (Saudi Arabia) and the Dead Sea (Israel and Jordan). Phylogenetic identification of the isolates was determined by 16S rRNA gene sequence analysis. The isolated Haloarchaea strains were able to grow on a mixture of benzoic acid, p-hydroxybenzoic acid, and salicylic acid (1.5 mM each) and a mixture of the polycyclic aromatic hydrocarbons, naphthalene, anthracene, phenanthrene, pyrene and benzo[a]anthracene (0.3 mM each). Evaluation of the extent of degradation of the mixed aromatic hydrocarbons demonstrated that the isolates could degrade these compounds in hypersaline media containing 20% NaCl. The strains were shown to reduce the COD of hypersaline crude oil reservoir produced waters significantly beyond that achieved using standard hydrogen peroxide treatment alone.     

Identification of Quarries Rehabilitation Scenarios: A Case Study Within the Metropolitan Area of Bari (Italy)

This paper addresses quarries rehabilitation issue within a Metropolitan Area. Areas where mining activity is carried out have been subjected to physical and environmental degradation linked both to pursue the building materials extraction and to the city expansion continuously asking for new areas to be developed with residential and service functions. These changes also occurred where environmental and landscape values are present. It has been therefore pointed out the issue of such areas redevelopment that, to be functionally reintegrated, must be consistently linked to the activities and the territorial local contexts characteristics. In this paper the quarries reuse issue is carried out through parameters identification able to define the quarries relationship with the neighboring towns and with their surroundings besides to identify their physical, environmental and landscaping characteristics. Quarry reuse alternatives have been identified among those consistent with the rehabilitation goals, as defined by the planning sector and internationally approved, while their selection is derived from the application of a two-step methodology: a multi-criteria analysis related to punctual parameters at a "site-specific" level, followed by a further territorial indicators checking over the wide area. This application has led to socially accepted results identifying the examined quarries for reuses ranging from agricultural-forestry and urban to functional or naturalistic. The proposed method has also proved to be suitable to address the abandoned quarries reuse problem with a systemic and consultative approach, as it is able to correlate the many variables present in the social and spatial complexity of the Metropolitan Areas.     

Furniture wood wastes: Experimental property characterisation and burning tests

Referring to the industrial wood waste category (as dominant in the provincial district of Pesaro-Urbino, Marche Region, Italy), this paper deals with the experimental characterisation and the carrying out of non-controlled burning tests (at lab- and pilot-scale) for selected “raw” and primarily “engineered” (“composite”) wood wastes.The property characterisation has primarily revealed the following aspects: potential influence on moisture content of local weather conditions at outdoor wood waste storage sites; generally, higher ash contents in “engineered” wood wastes as compared with “raw” wood wastes; and relatively high energy content values of “engineered” wood wastes (ranging on the whole from 3675 to 5105 kcal kg⁻¹ for HHV, and from 3304 to 4634 kcal kg⁻¹ for LHV).The smoke qualitative analysis of non-controlled lab-scale burning tests has primarily revealed: the presence of specific organic compounds indicative of incomplete wood combustion; the presence exclusively in “engineered” wood burning tests of pyrroles and amines, as well as the additional presence (as compared with “raw” wood burning) of further phenolic and containing nitrogen compounds; and the potential environmental impact of incomplete industrial wood burning on the photochemical smog phenomenon.Finally, non-controlled pilot-scale burning tests have primarily given the following findings: emission presence of carbon monoxide indicative of incomplete wood combustion; higher nitrogen oxide emission values detected in “engineered” wood burning tests as compared with “raw” wood burning test; and considerable generation of the respirable PM₁ fraction during incomplete industrial wood burning.     

Novel imazethapyr detoxification applying advanced oxidation processes

Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O?), and hydrogen peroxide tied to UV-irradiation (H?O?/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed. Ozonation joined to UV-irradiation (O?/UV), ozonation joined to titanium dioxide photo-catalysis (TiO?/UV+O?), sole photo-catalysis (TiO?/UV), and photo-catalysis reinforced with hydrogen peroxide-oxidation (TiO?/UV+H?O?) were characterized by a faster degradation and rapid formation of a lot of small molecules, which were quickly degraded to complete mineralization. The most effective oxidation methods were those using titanium dioxide photo-catalysis enhanced either by ozonation or hydrogen peroxide. Most of all, these last processes were useful to avoid the development of dangerous by-products.     

Safer management of process changes in chemical reactors

Nowadays many chemical industries are SMEs where multi-purpose batch or semi-batch reactors are commonly used. Vent sizing for realistic runaway scenario is not an easy task for such enterprises since they have usually few resources and use multi-purpose reactors with fast process turnovers. As a consequence these batch and semi-batch reactors are usually equipped with emergency relief systems sized once forever when the reactor is designed. This can lead to a large underestimation of the vent area in case of runaway reactions occurring when processes different from the ones considered for originally sizing the vent are carried out.The approach proposed in this work aims to identify the maximum reactor load leading to safe conditions even in case of runaway phenomena to be handled with the emergency relief system already installed (or even with a smaller vent area). This approach allows avoiding the change of the emergency relief system with a larger vent area (as required every time a new more hazardous process has to be carried out on existing reactors) at the price of lower plant productivity.     

Material and energy recovery in integrated waste management systems. An evaluation based on life cycle assessment

This paper reports the environmental results, integrated with those arising from mass and energy balances, of a research project on the comparative analysis of strategies for material and energy recovery from waste, funded by the Italian Ministry of Education, University and Research. The project, involving the cooperation of five University research groups, was devoted to the optimisation of material and energy recovery activities within integrated municipal solid waste (MSW) management systems. Four scenarios of separate collection (overall value of 35%, 50% without the collection of food waste, 50% including the collection of food waste, 65%) were defined for the implementation of energetic, environmental and economic balances. Two sizes of integrated MSW management system (IWMS) were considered: a metropolitan area, with a gross MSW production of 750,000 t/year and an average province, with a gross MSW production of 150,000 t/year. The environmental analysis was conducted using Life Cycle Assessment methodology (LCA), for both material and energy recovery activities. In order to avoid allocation we have used the technique of the expansion of the system boundaries. This means taking into consideration the impact on the environment related to the waste management activities in comparison with the avoided impacts related to the saving of raw materials and primary energy. Under the hypotheses of the study, both for the large and for the small IWMS, the energetic and environmental benefits are higher than the energetic and environmental impacts for all the scenarios analysed in terms of all the indicators considered: the scenario with 50% separate collection in a drop-off scheme excluding food waste shows the most promising perspectives, mainly arising from the highest collection (and recycling) of all the packaging materials, which is the activity giving the biggest energetic and environmental benefits. Main conclusions of the study in the general field of the assessment of the environmental performance of any integrated waste management scheme address the importance of properly defining, beyond the design value assumed for the separate collection as a whole, also the yields of each material recovered; particular significance is finally related to the amount of residues deriving from material recovery activities, resulting on average in the order of 20% of the collected materials.     

Evaluation of groundwater contamination in a coastal area of south-eastern Sicily

This investigation was under taken to evaluate the groundwater resources contamination due to intensive agricultural practices (particularly greenhouses). The study-area is located in the coastal area of the Ragusa province (South-East Sicily), where numerous existing greenhouses may cause the contamination of groundwater systems (unconfined and confined aquifers) beneath the cropped land. The pollution risk is mainly related with the seepage process of macro-elements nitrogen (N), phosphorus (P), potassium (K), held in the irrigation water and the massive use of fertilizers and pesticides, that may pass through the unsaturated zone of the soil profile. Moreover, the area is characterized by the presence of several wells (about 15 wells/km2) for agricultural use that cause the aquifer overexploitation and the consequent risk of seawater intrusion. The agriculture practices adopted in the study area (irrigation volumes, fertilizer concentrations, use of pesticides…) were monitored since February 2009; moreover, the pollution risk of the aquifers was evaluated through the analysis of groundwater water samples collected (monthly) in the monitoring wells; in particular, nitrogen compounds, soluble phosphorous (PO?2?), potassium, as well as the main pesticides commonly used in the study area, were measured.The results show that electrical conductivity and chloride concentration values can cause reduction of production and leaf damage problems, respectively, for most of the monitored farm systems. The high nitrogen compounds concentrations observed in the monitored wells can cause health and environmental problems. Moreover high pesticide contamination of groundwater was found in two of the five monitored wells.