Catalytic reduction of vat and sulfur dyes with hydrogen

Vat and sulfur dyes must be reduced to their leuco forms before application. Since this process is currently carried out using irreversible reducing chemicals, it involves high economic and environmental costs. Here we show that reduction can alternatively be performed in an alkaline bath at room temperature by using H₂ activated by a Pd catalyst. Sulfur dyes are thus directly reduced, whereas vat dyes require an electron transfer mediator. This alternative reaction can also be driven using H₂ at sub-atmospheric pressures. It further avoids all drawbacks raised by electrolytic reductions, so far suggested as alternative green processes.     

Characterization of dissolved organic matter from saline soils by fluorescence spectroscopy

In this paper hydrophilic (HI) and hydrophobic (HO) fractions of dissolved organic matter (DOM) extracted from soils at different degrees of salinisation were characterised by means of fluorescence spectroscopy in the emission, excitation and synchronous-scan modes. Results provided evidence of the different chemical nature of DOM fractions and allowed to distinguish hydrophilic and hydrophobic fractions extracted from the same soil substrate. The strong decrease in fluorescence intensity observed with the increasing salinity of the soils can be utilised to obtain information on the salinity level of different soil substrates by comparison of spectral fluorescence intensities.     

Climate and conflicts: the security risks of global warming

Since the publication of the fourth assessment report of the Intergovernmental Panel on Climate Change in 2007, the securitization of global warming has reached a new level. Numerous public statements and a growing research literature have discussed the potential security risks and conflicts associated with climate change. This article provides an overview of this debate and introduces an assessment framework of climate stress, human security and societal impacts. Key fields of conflict will be addressed, including water stress, land use and food security, natural disasters and environmental migration. A few regional hot spots of climate security will be discussed, such as land-use conflicts in Northern Africa; floods, sea-level rise and human security in Southern Asia; glacier melting and water insecurity in Central Asia and Latin America; water conflicts in the Middle East; climate security in the Mediterranean; and the potential impact on rich countries. Finally, concepts and strategies will be considered to minimize the security risks and move from conflict to cooperation in climate policy.     

Microbial degradation of two carbamate insecticides and their main metabolites in soil

Degradation studies in soil of the insecticides aldicarb and carbofuran and their metabolites (aldicarb sulfoxide, aldicarb sulfone; 3-ketocarbofuran and 3-hydroxycarbofuran) were carried out using laboratory systems under controlled conditions (temperature, water content, light). The insecticides were added to soil samples and subsamples of the soil were analyzed at different times to assess both the bacterial abundance and the concentration of the different chemicals. The epifluorescence direct count method was applied to the subsamples to estimate microorganism numbers (N/g soil). Untreated samples of soil were used as controls for evaluating the effects of the application of the insecticides on microbial abundance. Subsamples treated with the pesticides were analyzed using HPLC and the DT 50 s of the different compounds studied were calculated. The DT 50 values show that neither the parent compounds nor the transformation products have a high persistence in soil and there is a general increase in the concentration of microorganisms as the pesticides diminish.     

Ecosystem functioning approach applied to a large contaminated coastal site: the study case of the Mar Piccolo of Taranto (Ionian Sea)

Knowledge on ecosystem functioning can largely contribute to promote ecosystem-based management and its application. The Mar Piccolo of Taranto is a densely populated area at a high risk of environmental crisis. Here, planktonic primary production (PP) and heterotrophic prokaryotic production (HPP) were measured as proxies of functioning in three sampling sites located in two inlets at different levels of industrial contamination, during three sampling surveys (June 2013, February and April 2014). To have a better overall view and provide some insights into the benthic-pelagic coupling, we integrated PP and HPP in the water column with those in the sediments and then discussed this with the origin of the organic matter pools based on analysis of stable isotopes. Heavy metals and polychlorobiphenyls (PCBs) were also analysed in the surface (1 cm) sediment layer and related to the overall ecosystem functioning. Multidimensional scaling (MDS) analysis, based on the main data, clearly separated the second inlet from the first one, more severely impacted by anthropogenic activities. The stable isotope mixing model suggested the prevalent terrestrial/riverine origin of the particulate organic matter pools (mean 45.5 %) in all sampling periods, whereas phytoplankton contributed up to 29 % in February. Planktonic PP and HPP rates followed the same pattern over the entire study period and seemed to respond to phytoplankton dynamics confirming this community as the main driver for the C cycling in the water column. On the contrary, benthic PP rates were almost negligible while HPP rates were lower or comparable to those in the water column indicating that although the Mar Piccolo is very shallow, the water column is much more productive than the surface sediments. The sediment resuspension is likely responsible for a pulsed input of contaminants into the water column. However, their interference with the proper functioning of the pelagic ecosystem seems to be limited to the bottom layers.     

River pollution from non-point sources: a new simplified method of assessment

Assessment of the pollution of water bodies from non-point sources is a complex data- and time-consuming task. The potential non-point pollution index (PNPI), is a new tool designed to assess the global pressure exerted on rivers and other surface water bodies by different land uses. The main feature of PNPI is the wide availability of its input data. Very detailed input maps, often lacking over many areas, are not needed for PNPI calculation. As a consequence of the input data used, the modelling of physical reality and of processes is heavily simplified. The authors counterbalanced such a simplification using an 'expert system' approach. The system bypasses the accurate representation of the physical reality to assess globally the pollution potential of different land uses according to the judgement of scientists. The scientific community proposes many models for depicting the dynamics of pollutants coming from diffuse sources. Most of them can be grouped into two broad categories: statistical models and physically based models. PNPI belongs to neither of the above-mentioned groups. PNPI is a GIS-based, watershed-scale tool designed to inform decision makers and public opinion about the potential environmental impacts of different land management scenarios. PNPI applies the multicriteria technique to pollutant dynamics and water quality. The pressure exerted on water bodies by diffuse pollution coming from land units is expressed as a function of three indicators: land use, run-off and distance from the river network. They are calculated from land use data, geological maps and a digital elevation model (DEM). The weights given to different land uses and to the three indicators were set according to experts' evaluations and allow calculation of the value of the PNPI for each node of a grid representing the watershed; the higher the PNPI of the cell, the greater the potential impact on the river network. The output of the calculation is presented in the form of maps that highlight areas that are more likely to produce pollution. Last, possibilities, strategies and results of the validation of the PNPI are described. In the authors' view, the explicit link between land use and potential pollution on which PNPI is based, together with its high communication potential, make it particularly interesting for a participatory and integrated approach to land management and environmental protection.     

Analysis of metals and EOX in sludge from municipal wastewater treatment plants: a case study

The monitoring of extractable organic halogen (EOX) and heavy metal contents in sludge coming from 10 different municipal wastewater treatment plants (MWWTP) located in Friuli Venezia Giulia (Italy) is reported. In this work, sludge samples drawn from sludge treatment units have been digested and analyzed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) for metal evaluation. Samples were also extracted and analyzed by microcoulometric titrations, following modified DIN 38414 T17 standard, for EOX analysis. Analytical results showed a slight enrichment of the contents of certain metals (Cd< 2mg/kg, Cr< 51.5mg/kg, Cu<105.8 mg/kg, Hg<1.4 mg/kg, Ni<35.9 mg/kg, Pb<58.7 mg/kg, Zn<410.1 mg/kg, Ba<317.1 mg/kg, Co<1 mg/kg, Mo< 5 mg/kg, Mn<106.7 mg/kg), so almost all of the sludge would be suitable for agricultural use following Italian and European regulations. The evaluation of EOX was carried out by using hexane and ethyl acetate as extraction solvents, and a measurable organic halogen content (ranging from 0.31 to 39.5 mg Cl/kg DM) was clearly detected in the sludge. The lowest concentrations of EOX were found in sludge coming from the smallest MWWTPs, which is to be considered more suitable for agricultural use. Additionally, analytical assays on composts, peat and soils were performed to compare EOX concentrations between these matrices and sludge.     

Fate of diuron and linuron in a field lysimeter experiment

The environmental fate of herbicides can be studied at different levels: in the lab with disturbed or undisturbed soil columns or in the field with suction cup lysimeters or soil enclosure lysimeters. A field lysimeter experiment with 10 soil enclosures was performed to evaluate the mass balance in different environmental compartments of the phenylurea herbicides diuron [3-(3,4-diclorophenyl)-1,1-dimethyl-urea] and linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea]. After application on the agricultural soil, the herbicides were searched for in soil, pore water, and air samples. Soil and water samples were collected at different depths of the soil profile and analyzed to determine residual concentrations of both the parent compounds and of their main transformation products, to verify their persistence and their leaching capacity. Air volatilization was calculated using the theoretical profile shape method. The herbicides were detected only in the surface layer (0-10 cm) of soil. In this layer, diuron was reduced to 50% of its initial concentration at the end of the experiment, while linuron was still 70% present after 245 d. The main metabolites detected were DCPMU [3-(3,4-dichlorophenyl)-1-methylurea] and DCA (3,4-dichloroaniline). In soil pore water, diuron and linuron were detected at depths of 20 and 40 cm, although in very low concentrations. Therefore the leaching of these herbicides was quite low in this experiment. Moreover, volatilization losses were inconsequential. The calculated total mass balance showed a high persistence of linuron and diuron in the soil, a low mobility in soil pore water (less than 0.5% in leachate water), and a negligible volatilization effect. The application of the Pesticide Leaching Model (PELMO) showed similar low mobility of the chemicals in soil and water, but overestimated their volatilization and their degradation to the metabolite DCPMU. In conclusion, the use of soil enclosure lysimeters proved to be a good experimental design for studying mobility and transport processes of herbicides in field conditions.