Pt/Mg-Ce-O catalyst for NO/H<Subscript>2</Subscript>/O<Subscript>2</Subscript> lean de-No<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reaction

The NO/H₂/O₂ reaction was studied under oxidizing conditions in the 100-400 °C range over 0.1 wt% Pt supported on various metal oxides such as MgO, CeO₂, SiO₂, La₂O₃, CaO, Y₂O₃ and TiO₂. The Pt/MgO and Pt/CeO₂ catalysts showed good catalytic behaviours. Here, we find that the Pt/Mg-Ce-O catalyst, prepared from MgO and CeO₂ by the sol-gel method, is a very active and selective catalyst towards N₂ formation in the whole 100–400 °C range. This catalyst appears to be the most active, selective and stable one ever reported in the literature for the NO/H₂/O₂ reaction, even in the presence of 5%v H₂O or 20 ppmv of SO₂ in the feed stream.Selected article from the Regional Symposium on Chemistry and Environment, Krusevac, Serbia, June 2003, organised by Dr. Branimir Jovancicevic.     

Optimisation of a microbial bioassay for contaminated soil monitoring: bacterial inoculum standardisation and comparison with Microtox assay

This work represents the first step to set up a toxicity testing procedure and to evaluate the sensitivity of the test microorganism to several classes of environmental pollutants. First, three different techniques were employed to standardise the microbial inoculum, then two different toxicity assessment protocols have been compared: Microtox and a dehydrogenase (DHase) activity inhibition test. The main goal was the optimisation of a microbial bioassay based on the dehydrogenase activity (DHase) inhibition in Pseudomonas fluorescens bacterial strain ATCC 13525. Triphenyl tetrazolium chloride (TTC) was used as electron acceptor and its reduction produces Triphenyl formazane (TPF). The P. fluorescens DHase inhibition bioassay was investigated for being a reliable and rapid method for assessing toxicity. The optimisation of the operating conditions resulted in a repeatable bioassay. Then, P. fluorescens and Vibrio fischeri sensitivity were firstly compared by testing Zn++, one of the reference compounds for Microtox test. In addition, other compounds (Ni++, Cd++, Cu++, phenol) were also tested with both bioassays. A high statistical significance of data was obtained with the logistic curve. The present work has demonstrated that P. fluorescens is as sensitive as Microtox culture (V. fischeri), for some of the metal ions. With reference to organic compounds, the lower sensitivity of P. fluorescens to phenol makes its use difficult in organic polluted samples.     

Effect of sewage amendment on the dissipation of terbuthylazine,its degradation compound desethyl-terbuthylazine,and S-metolachlor in a field study

This study evaluates the effect of sewage amendment (SA) on the dissipation of terbuthylazine, its degradation compound desethyl-terbuthylazine, and S-metolachlor in the soil. The experiment was conducted at Padua Experimental Farm (Italy). Herbicides dissipation was evaluated in soils differently fertilized for three years: with inorganic fertilizer, with sewage sludge, and with a combination of them. Terbuthylazine and S-metolachlor were applied on sorghum as a formulated product at a dose of 2.8?L ha^?1, and their dissipation was followed for 2.5 months. The concentrations of herbicides and one metabolite in soil were analyzed by liquid chromatography-mass spectrometry. The dissipation of terbuthylazine and S-metolachlor followed a pseudo first order kinetics; they dissipated faster in soil amended only with inorganic fertilizer than in soils amended with sewage or sewage?+?inorganic fertilizer. The reduction in mineralization of the herbicides after sewage addition can be attributed to the reduced herbicide availability to microorganisms. The degradation of terbuthylazine led to the formation of desethyl-terbuthylazine. SA slowed down the formation and the degradation of desethyl-terbuthylazine, leading to a higher amount measured at the end of the incubation. These findings have practical implications for the assessment of the environmental fate of terbuthylazine and S-metolachlor in agricultural areas.     

Efficient use of Fe metal as an electron transfer agent in a heterogeneous Fenton system based on Fe0/Fe3O4 composites

In this work a novel heterogeneous Fenton system based on Fe(0)/Fe3O4 composites is described. The composites with several Fe(0)/Fe3O4 ratios were prepared by two different methods, i.e. mechanical alloying of Fe(0) and Fe3O4 powders and controlled reduction of Fe3O4 with H2. Reaction studies and detailed Conversion Electron M?ssbauer surface characterization of the composites Fe(0)/Fe3O4, Fe(0), Fe3O4, alpha-Fe2O3 and gamma-Fe2O3 suggested that Fe2+surf species are essential to produce an active Fenton system. Kinetic studies for the oxidation of the dye methylene blue, used as an organic model molecule, and for the peroxide decomposition suggest that the reactions proceed via HO* radicals generated from Fe2+surf species and H2O2 in a Fenton like mechanism. The increase in activity caused by the addition of Fe(0) is discussed in terms of a creation of Fe2+surf species during the preparation of the composite and by an electron transfer mechanism from Fe(0) to Fe3+surf during the Fenton reaction to regenerate the Fe2+surf active species.     

Methylmercury and total mercury in estuarine organisms from Rio de Janeiro, Brazil

Guanabara Bay (GB), located in the Rio de Janeiro State, is still a productive estuary on the south-eastern Brazilian coast. It is an ecosystem heavily impacted by organic matter, oil and a number of other toxic compounds, including Hg. The present study aimed to comparatively evaluate the aquatic total mercury (THg) and MeHg contamination, and the ratios of MeHg to THg (% MeHg), in 3 species of marine organisms, Micropogonias furnieri-carnivorous fish (N = 81), Mugil spp.--detritivorous fish (N = 20) and Perna perna--filter-feeding bivalves (N = 190), which are widely consumed by the population. A total of 291 specimens were collected at the bay in different periods between 1988 and 1998. THg concentrations were determined by cold vapour AAS with stannous chloride as a reducing agent. MeHg was extracted by dithizone-benzene and measured by GC-ECD. Analytical quality was checked through certified standards. All organisms presented both low THg and MeHg concentrations and they were below the maximum limit of 1,000 micrograms Hg.kg-1 wet wt. as established for human intake of predatory fish by the new Brazilian legislation. Carnivorous fish showed higher THg and MeHg concentrations, and also % MeHg in muscle tissues, than organisms with other feeding habits and lower trophic levels. The average of THg concentrations in carnivorous fish was 108.9 +/- 58.6 micrograms.kg-1 wet wt. (N = 61) in 1990 and 199.5 +/- 116.2 micrograms.kg-1 wet wt. (N = 20) in 1998, but they presented different total length and body weights. The average THg content in detritivorous fish was 15.4 +/- 5.8 micrograms.kg-1 wet wt., whereas THg concentrations ranged from 4.1 to 53.5 micrograms.kg-1 wet wt. for the molluscs. The THg and MeHg contents of mussel varied according to the sampling point and water quality. MeHg concentration in detritivorous fish was similar to MeHg concentration in molluscs, but there was a significant difference in the MeHg/THg ratio: the carnivorous fish presented higher MeHg percentages (98%) than the detritivorous fish (54%) and the molluscs (33%). Weight-normalised average concentration of THg in carnivorous fish collected in 1990 (0.18 +/- 0.08 microgram.g-1/0.7 kg wet wt.) and in 1998 (0.16 +/- 0.09 microgram.g-1/0.7 kg wet wt.) presented no significant difference (t = 1.34; P < 0.5). In conclusion, the low THg and MeHg concentrations in the organisms from the GB ecosystem, are related to its eutrophic conditions and elevated amounts of suspended matter. In this situation, Hg could be strongly complexed or adsorbed by the particulate, which would dilute the Hg inputs and reduce its residence time in the water column, with a consequent decrease in its availability to organisms.     

Evaluation of soil temperature effect on herbicide leaching potential into groundwater in the Brazilian Cerrado

The effect of annual variations in the daily average soil temperatures, at different depths, on the calculation of pesticide leaching potential indices is presented. This index can be applied to assess the risk of groundwater contamination by a pesticide. It considers the effects of water table depth, daily recharge net rate, pesticide sorption coefficient, and degradation rate of the pesticide in the soil. The leaching potential index is frequently used as a screening indicator in pesticide groundwater contamination studies, and the temperature effect involved in its calculation is usually not considered. It is well known that soil temperature affects pesticide degradation rates, air-water partition coefficient, and water-soil partition coefficient. These three parameters are components of the attenuation and retardation factors, as well as the leaching potential index, and contribute to determine pesticide behavior in the environment. The Arrhenius, van't Hoff, and Clausius-Clapeyron equations were used in this work to estimate the soil temperature effect on pesticide degradation rate, air-water partition coefficient, and water-soil partition coefficient, respectively. The relationship between leaching potential index and soil temperature at different depths is presented and aids in the understanding of how potential pesticide groundwater contamination varies on different climatic conditions. Numerical results will be presented for 31 herbicides known to be used in corn and soybean crops grown on the municipality of S?o Gabriel do Oeste, Mato Grosso do Sul State, Brazil.     

Speciation of heavy metals in estuarine sediments in the northeast of Brazil

An analytical procedure involving a three-step sequential extraction was used to determine the chemical association of heavy metals (Zn, Cr, Mn and Fe) with the major phases (exchangable, reducible and oxidizable) in samples from a fishpond of estuarine sediments. The pond is located in the Capibaribe River estuary, within the boundaries of the city of Recife, in the State of Pernambuco in the northeast of Brazil. The total metal content was determined as well. All metals were extracted from the residual fraction at a percentage greater than 50%.     

Aqueous solubility, Henry's law constants and air/water partition coefficients of n-octane and two halogenated octanes

New data on the aqueous solubility of n-octane, 1-chlorooctane and 1-bromooctane are reported between 1 degree C and 45 degrees C. Henry's law constants, K(H), and air/water partition coefficients, K(AW), were calculated by associating the measured solubility values to vapor pressures taken from literature. The mole fraction aqueous solubility varies between (1.13-1.60)x10(-7) for n-octane with a minimum at approximately 23 degrees C, (3.99-5.07)x10(-7) for 1-chlorooctane increasing monotonically with temperature and (1.60-3.44)x10(-7) for 1-bromooctane with a minimum near 18 degrees C. The calculated air-water partition coefficients increase with temperature and are two orders of magnitude lower for the halogenated derivatives compared to octane. The precision of the results, taken as the average absolute deviations of the aqueous solubility, the Henry's law constants, or the air/water partition coefficients, from appropriate smoothing equations as a function of temperature is of 3% for n-octane and of 2% and 4% for 1-chlorooctane and 1-bromooctane, respectively. A new apparatus based on the dynamic saturation column method was used for the solubility measurements. Test measurements with n-octane indicated the capability of measuring solubilities between 10(-6) and 10(-10) in mole fraction, with an estimated accuracy better than +/-10%. A thorough thermodynamic analysis of converting measured data to air/water partition coefficients is presented.     

The determinants mostly disclosed by companies that are members of the Carbon Disclosure Project

Concerns about climate change as a result of anthropic actions have led to an increase in the volume of information disclosed about it in the reports of companies that are members of the Carbon Disclosure Project (CDP). In this context, the factors most disclosed remain obscure due to both the complexity of climate change impacts and the stakeholders’ different interests. This study aims to identify which factors are most disclosed in the reports of companies that are members of CDP. For this purpose, it is necessary to investigate if the factors indicated by managers and experts are the main ones disclosed in the reports of Brazilian companies that are members of CDP, as well as to identify which companies stand out in climate change disclosure based on these factors. To this end, 463 reports submitted by 48 companies between 2014 and 2016 were examined and 32 factors were investigated using the NVivo® software. Some companies submitted reports with unified titles, which reduced the sample. The results indicate that certain factors—prevention of pollution, prevention of loss, management of environmental assets, volume of greenhouse gas (GHG) emissions, and climate change strategy—account for 50.03% of the total volume of information disclosed about climate change. The main lesson learned from this research is that climate change mitigation strategy is strongly supported by the evidence of corporate annual reports, and it has relation with the following determinant factors: pollution prevention, loss prevention, environmental asset management, GHG emissions, and the strategy chosen by the companies to deal with climate change. Due to the low volume of research related to loss prevention and pollution prevention, we have identified that little attention has been paid to these items. Based on our results, we recommend that climate change mitigation strategies begin to consider these determinant factors in their structure because both have a strong influence in demonstrating how companies are managing these factors for stakeholders. Therefore, companies can benefit from this data to manage their resources for the maintenance of the social contract (legitimacy) through the factors most disclosed, especially companies with lower scores on the scale of ranking presented. Hence, stakeholders can have access to more information on strategies that mitigate climate change and help companies improve the disclosure of the actions that contribute to reduction of GHG emissions.     

Disclosure of climate risk information by the world’s largest companies

The risks related to global climate change are seen as threats to companies, taking into consideration their impact on the return on investment. In order to mitigate climate risk and introduce new opportunities to financiers, companies need to identify, manage, and report climate risks. The purpose of this paper is to investigate the climate risks disclosed by the 100 largest companies in the world, according to the Bloomberg and Price Waterhouse Coopers (PwC 2015) classification, and identify some characteristics of these companies that explain the disclosure level of such information. Preliminary results revealed that of the companies investigated, 14% did not disclose any climate risk information in the Carbon Disclosure Program (CDP) report. Also, from the companies that disclosed information according to the Global Reporting Initiative (GRI), 9.9% did not provide information regarding policies, actions, and strategies for mitigating the risks related to climate change. The results shown by the content analysis suggested that, in general, there is still a low level of disclosure about climate risks by these companies. The final results through econometric instruments and statistical tests indicate that the size of the company or the fact that corporations are from developed countries do not necessarily explain the level of information disclosed. However, the activity sector, the continent, and the efficiency of the Board of Directors are factors that strongly explain the level of climate risk disclosure. We conclude that more effort is needed to encourage an engaging attitude from corporations to develop actions, policies, and strategies to mitigate climate change risks and threats. In addition, the world’s largest companies should make a greater investment in climate risk disclosure.