Comparison of criteria for prediction of runaway reactions in the sulphuric acid catalyzed esterification of acetic anhydride and methanol

Loss of temperature control is one of the major reasons that can lead to runaway reaction. This occurrence is commonly named thermal runway. The aim of this paper is the application of thermal runaway criteria in order to predict the onset of runaway phenomena and define the range of stability related to operating conditions in the reactor, with specific reference to the esterification of acetic anhydride and methanol catalysed by sulphuric acid tested in isoperibolic conditions. The isoperibolic calorimeter has also been used to obtain thermodynamic, kinetic and physical chemistry data necessary to develop a model for the reaction. Some runaway criteria applied in this work require a model for the process, so a model for the analyzed system been developed.Because of the modest reaction enthalpy and low activation energy this reacting system provide a severe test to the runaway criteria.In this work, various runaway criteria have been applied to the experimental and simulated data and the results obtained have been compared.     

Dynamic of functional microbial groups during mesophilic composting of agro-industrial wastes and free-living (N2)-fixing bacteria application

Although several reports are available concerning the composition and dynamics of the microflora during the composting of municipal solid wastes, little is known about the microbial diversity during the composting of agro-industrial refuse. For this reason, the first parts of this study included the quantification of microbial generic groups and of the main functional groups of C and N cycle during composting of agro-industrial refuse. After a generalized decrease observed during the initial phases, a new bacterial growth was observed in the final phase of the process. Ammonifiers and (N₂)-fixing aerobic groups predominated outside of the piles whereas, nitrate-reducing group increased inside the piles during the first 23 days of composting. Ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB), showed an opposite trend of growth since ammonia oxidation decreased with the increase of the nitrite oxidation activity. Pectinolytics, amylolytics and aerobic cellulolytic were present in greater quantities and showed an upward trend in both the internal and external part of the heaps.Several free-living (N₂)-fixing bacteria were molecularly identify as belonging especially to uncommon genera of nitrogen-fixing bacteria as Stenotrophomonas, Xanthomonas, Pseudomonas, Klebsiella, Alcaligenes, Achromobacter and Caulobacter. They were investigated for their ability to fix atmospheric nitrogen to employ as improvers of quality of compost. Some strains of Azotobacter chrococcum and Azotobacter salinestris were also tested. When different diazotrophic bacterial species were added in compost, the increase of total N ranged from 16% to 27% depending on the selected microbial strain being used. Such microorganisms may be used alone or in mixtures to provide an allocation of plant growth promoting rhizobacteria in soil.     

Influence of large-spectrum environmental contamination on the micro-meiobenthic assemblages in harbour sediments of the ligurian sea (W Mediterranean)

The concentration of a large spectrum of environmental contaminants (PCBs, PAHs, pesticides and metals) was assessed in surface sediments of two Ligurian harbours (Sanremo and Alassio, NW Mediterranean Sea, Italy) and their relative impact on micro-meiobenthic assemblages was analysed. Concentration, distribution and relative importance of the different contaminants varied considerably between harbours in relation to the different anthropic activities and contamination sources. Results from Principal Component Analysis indicated that high levels of contaminants were typically correlated with low micro-meiobenthic abundance in the sediment. Heavy metals and the organic enrichment were the main factors affecting the distribution and abundance of the bacterial and meiofaunal assemblages in Alassio harbour, whereas hydrocarbons and pesticides played a major role in Sanremo sediments. Neither the bacteria density nor the meiofauna abundance were dependent on sediment grain size, suggesting that micro-meiobenthic parameters may be under the influence of other variables. Our results suggest that high concentrations of contaminants independently from their source or typology are responsible for the impact observed on micro-meiobenthic assemblages in these harbours.     

EPR monitoring of the bioavailability of an organic xenobiotic (4-hydroxy-TEMPO) in model clay suspensions and pastes

Electron paramagnetic resonance spectroscopy is used to monitor the bioavailability of a nitroxide spin probe, 4-hydroxy-Tempo or Tempol, in Ca-hectorite suspensions and pastes, to bacteria capable of degrading this probe co-metabolically. In nutrient solutions with an initial probe concentration of 1.2 mM and in the absence of hectorite, bacteria are able to denature Tempol and eliminate its paramagnetic signal within 48 h. In the presence of hectorite and after flocculation, the effect of bacteria is significantly delayed, but almost complete denaturation still occurs, after roughly 120 h. When hectorite is added but the bacterial/clay suspension is not centrifuged, Tempol denaturation levels off after about 24 h and reaches a plateau with approximately 45% of Tempol remaining. This plateau does not constitute evidence of limited bioavailability, as is widely assumed, since subsequent addition of nutrients causes the denaturation reaction to proceed to a second plateau, with merely 10% of Tempol remaining.     

pp´DDT and pp´DDE Accumulation in a Food Chain of Lake Maggiore (Northern Italy): Testing Steady-State Condition

- DOI: http://dx.doi.org/10.1065/espr2006.01.010 Background, Aims and Scope Although pp'DDT usage was strongly limited or banned in most parts of the world during the last three or four decades, the parent compound, its homologues and their metabolites still occur at levels which might pose a risk for many ecosystem components. A case of DDT pollution of industrial origin was discovered in 1996 in Lake Maggiore, the second largest (212 km2) and deepest (370 m) lake in Italy, causing concern for wildlife and human health. The extensive monitoring of many biotic and abiotic compartments which followed from 1998 in order to assess the pollution level and its trend in time, provided a great availability of data referring to DDT contamination of the different fish species of the lake. In this study, the recent contamination levels in selected fish species were compared to those measured in 1998 to evaluate the temporal pollution trend of the lake and its natural recovery, given that no remediation measures were carried out on the contaminated soils and sediments in this time span. Moreover, a modelling approach to test the equilibrium condition between water and pelagic fish species was used. Analytical results of pp'DDT and pp'DDE concentrations in lake water were used as input data in the bioenergetic model by Connolly & Pedersen (1988) to calculate concentrations in two fish species and to compare the predicted and the measured contamination. Methods Sampling and analytical determination of DDT homologues in lake water: Five water sampling campaigns were carried out from May 2002 to February 2004 in three sampling sites of Lake Maggiore. Suspended and dissolved pollutants were determined separately. Quantitative DDT homologue analyses were performed by HRGC coupled with ECD detection by the external standard method. Single water extracts were put together in correspondence with the stratification zones of the water column inferred on the basis of the temperature profile to improve analytical sensitivity. Selection of fish data: Concentrations of DDT and DDE in fishes were selected from recent literature (CIPAIS 2003, 2004). Bioaccumulation model: The bioenergetic model proposed by Connolly & Pedersen (1988) was used to assess the bioaccumulation of pp'DDT and pp'DDE of Alosa fallax (landlocked shad) and Coregonus spp. (whitefish), selected among the different species as representative of a secondary consumer level. Results and Discussion The average concentrations of pp'DDT and pp'DDE in water to be used as input data in the bioenergetic model were obtained considering all the concentrations measured at the three sampling stations in the epylimnion where the fish species considered in this study spend most of their life. The resulting values were 0.05 and 0.16 ng/L for pp'DDT and pp'DDE, respectively. Average measured pp'DDT and pp'DDE concentrations in landlocked shad were 0.81 +/- 0.39 and 1.69 +/- 0.71 mg/kg lipids, respectively, and were 0.29 +/- 0.12 and 1.06 +/- 0.41 mg/kg lipids for the whitefish. Calculated and measured values turned out to be in quite good agreement for pp'DDT, while measured pp'DDE concentrations were higher than expected on the basis of the bioenergetic model in both species. Probably metabolic transformations of pp'DDT accumulated in fish tissues in the past are responsible for the observed differences between calculated and expected pp'DDE concentrations in fish. Conclusions Pelagic fishes of Lake Maggiore seem to maintain the DDT accumulated during their life time and the most efficient mechanism responsible for the fish population recoveries is probably their generation changes; for this reason, equilibrium models cannot be used until negligible pp'DDT concentrations are reached in fish tissues. Recommendations and Outlook The limit proposed for pp'DDT in water by the EU Directive 2000/60, which will come in force in 2008, is 0.2 ng/L, four times higher than the average concentration measured in Lake Maggiore waters. Nevertheless, concentrations measured in Lake Maggiore fish were very close and sometimes exceeded the Maximum residue limits (MRLs) settled by the Italian legislation for foods (0.1 mg/kg w.w. for fish containing 5–20% lipid). It seems, therefore, that the 'environmental quality standard' of 0.2 ng/L cannot guarantee the suitability of fish for human consumption.     

Meta-analysis of the differential effects of habitat fragmentation and degradation on plant genetic diversity

Genetic diversity is a key factor for population survival and evolution. However, anthropogenic habitat disturbance can erode it, making populations more prone to extinction. Aiming to assess the global effects of habitat disturbance on plant genetic variation, we conducted a meta-analysis based on 92 case studies obtained from published literature. We compared the effects of habitat fragmentation and degradation on plant allelic richness and gene diversity (equivalent to expected heterozygosity) and tested whether such changes are sensitive to different life-forms, life spans, mating systems, and commonness. Anthropogenic disturbance had a negative effect on allelic richness, but not on gene diversity. Habitat fragmentation had a negative effect on genetic variation, whereas habitat degradation had no effect. When we examined the individual effects in fragmented habitats, allelic richness and gene diversity decreased, but this decrease was strongly dependent on certain plant traits. Specifically, common long-lived trees and self-incompatible species were more susceptible to allelic richness loss. Conversely, gene diversity decreased in common short-lived species (herbs) with self-compatible reproduction. In a wider geographical context, tropical plant communities were more sensitive to allelic richness loss, whereas temperate plant communities were more sensitive to gene diversity loss. Our synthesis showed complex responses to habitat disturbance among plant species. In many cases, the absence of effects could be the result of the time elapsed since the disturbance event or reproductive systems favoring self-pollination, but attention must be paid to those plant species that are more susceptible to losing genetic diversity, and appropriate conservation should be actions taken.     

Reduction of silver solubility by humic acid and thiol ligands during acanthite (beta-Ag2S) dissolution

Precipitation of highly insoluble metal sulfide minerals like acanthite (beta-Ag2S) or red cinnabar (HgS) is in principle an effective means to reduce metal availability and toxicity in contaminated soils. Unfortunately, experiments have shown that red cinnabar may be solubilized in the presence of dissolved organic matter or thiol ligands. To determine whether the same applies to acanthite, a laboratory synthesized beta-Ag2S mineral was incubated for up to 3 weeks in the presence of KNO3, dissolved humic acids, cysteine, methionine and thiosulfate. XPS analysis identified Ag2O (52%), Ag2SO4 (8%) and Ag2S (40%) on the particle surfaces. Ag was released into solution in the presence of KNO3 and methionine, presumably from mixed-oxidation surface layers. Contrary to earlier results with cinnabar, however, humic acids reduced Ag concentrations in solution by about 75%, and cysteine and thiosulfate, each containing a free -SH functional group, almost completely suppressed Ag release into solution.     

Metal ion uptake from aqueous solution by olive stones: a carbon-13 solid-state nuclear magnetic resonance and potentiometric study.

The use of biomasses that result from the agriculture and food industries in removing heavy metals from wastewaters is attracting increasing interest. We present a joined potentiometric and cross polarization magic angle spinning (CP-MAS) carbon-13 (13C) nuclear magnetic resonance (NMR) study on the interaction of olive stones with copper(II), nickel(II), and cadmium(II). The potentiometric measurements allow both to distinguish two kind of basic sites in the olive stones and to postulate the coordination models for the three studied metals. The NMR spectral analysis allows the attribution of the different signals to the components of the olive stone matrix. A comparison of CP-MAS 13C NMR spectra of the samples after metal treatment suggests a specific complexation between metal ions and hydroxyl groups on guaiacyl and syringyl moieties.     

Development and pre-validation of a testosterone enzyme immunoassay (EIA) for predicting the sex ratio of immature loggerhead sea turtles (Caretta caretta) recovered along the western coast of the central Adriatic Sea

Plasma testosterone levels were evaluated, by validating and using a commercially available testosterone enzyme immunoassay (EIA) as an indicator of the sex of immature loggerhead turtles (Caretta caretta) recovered along the western coast of the central Adriatic Sea between November 2011 and February 2012. Testosterone levels were measured in blood samples collected from 28 immature turtles kept in short-term maintenance at the Fondazione Cetacea Rescue Centre (Italy). Overall, plasma testosterone ranged between 229.3 and 2628.6 pg ml^?1, suggesting that the EIA procedure is effective for determining androgen titers in immature loggerhead sea turtles. Analysis of the obtained data indicates an unbiased sex ratio supporting previous studies of juvenile loggerhead turtle sex ratios in the Mediterranean Sea. The present work can be considered a starting point for augmenting knowledge on the dynamics of juvenile loggerhead aggregations increasingly found in the northern-central Adriatic Sea and for promoting local management for conservation actions.