Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions around the world. Its thermal hazards may also be incurred by an incompatible reaction with other chemicals, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to these accidents by incompatibility and to discuss what might be formed by the upset situations. Thermal hazard analysis contained a solvent, propanone (CH₃COCH₃, so-called acetone), which was deliberately selected to mix with H₂O₂ for investigating the degree of thermal hazard. Differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to evaluate the thermal hazard of H₂O₂. The results indicated that H₂O₂ is highly hazardous while mixed with propanone, as a potential contaminant. The time to maximum rate (TMR) was used as emergency response time in the chemical industries. Therefore, TMR of H₂O₂ was calculated to be 70 min for runaway reaction (after T₀) and TMR of H₂O₂/propanone was discovered to be 27 min only. Fire and explosion hazards could be successfully lessened if the safety-related data are properly imbedded into manufacturing processes.     

Female courtship in the Banggai cardinalfish: honest signals of egg maturity and reproductive output?

Despite the vast literature on male courtship behaviour, little is known about the function and information content of female courtship behaviour. Female courtship behaviour may be important in many species, particularly where both sexes invest heavily in the offspring, and if such behaviours contain honest information regarding a females potential reproductive investment, they may be particularly important in male mate choice. Using observations of two female courtship behaviours (the rush and the twitch) from experimental pairings in the Banggai cardinalfish (Pterapogon kauderni), I addressed the question of whether these courtship behaviours contained information on female reproductive output (clutch weight) and egg maturity (proximity to spawning), traits commonly associated with male mate choice. I especially focused on the importance of these courtship behaviours in relation to other female characters, such as size and condition, using multiple regression. I found that one of these behaviours, the rush, was strongly associated with fecundity, whereas size, condition and the twitch were not. Further, I found that the twitch behaviour was associated with how close to actual spawning a female was. The results suggest that female courtship behaviour may convey highly important information in a mate choice context. I discuss the adaptive value of honest information in female courtship behaviour in light of these results.Communicated by K. Lindström     

A voltammetric screening method to determine ronidazole in bovine meat

Abstract

An original voltammetric screening method, employing glassy carbon electrode (GCE) with the differential-pulse voltammetry technique (DPV), has been developed to determine residues of the anti-parasitic agent Ronidazole (RNZ) in bovine meat. By using cyclic voltammetry (CV), it has been demonstrated that an irreversible cathodic process occurs at approximately ?0.740?V (vs. Ag|AgCl, KCl 3?mol L^?1) in a 0.100?mol L^?1 phosphate buffer at pH 6.5 as supporting electrolyte. Furthermore, the behavior of RNZ in CV indicates the occurrence of a diffusion mass transfer process to the working electrode surface. The RNZ reduction mechanism was proposed as a 6-electron transfer, similar to Metronidazole under the same pH range. Quantification of RNZ and method validation were then carried out by DPV. The relative standard deviation (RSD) were 3.21% for intraday precision of 10 consecutive repetitions and 6.78% for interday precision after five analysis. Limits of detection and quantification were also obtained, and the values were 0.107 and 0.358?mg kg^?1, respectively. The recovery percentage for three different concentrations of RNZ in the bovine meat matrix ranged between 98.1% and 100.3%. The method proved to be efficient for screening RNZ in bovine meat.     

Evaluation of multiple reactions in dilute benzoyl peroxide concentrations with additives using calorimetric technology

Benzoyl peroxide (BPO) is a typical organic peroxide widely used in food processing, particularly flour bleaching. Due to the unstable nature of the oxygen-oxygen bond in BPO, it readily reacts under even mid-low-temperature conditions. Lower concentrations of BPO are also potentially explosive, even when combined with acid or alkaline additives. Given the history of both potential and documented industrial accidents, this study investigates the thermal stability of various BPO concentrations when mixed with acid or alkaline solutions. In addition, differential and integral kinetic models were applied to verify that the apparent activation energy data from the differential scanning calorimetry experiments were valid. The results of autocatalysis reactions and nth-order reaction simulations presented characteristics consistent with the experimental findings. The findings in this paper can be used as a reference for BPO products that are mediated with either an acid or an alkaline solution during production, storage, transportation, or use.     

Influence of phytoplankton on complexing capacity of seawater†

Differential Pulse Anodic Stripping Voltammetry (DPASV) was employed to measure Apparent Copper Complexing Capacity (L_t) and Stability Constants (K_s) of related cupric complexes of cell exudates of the phytoplanktonic alga Dunaliella salina. Three natural seawater samples collected 0.1, 2, 5 miles off the Tyrrhenian coast were used as culture medium. The measurements were carried out 1h and 7 days after the inoculum. Furthermore, on one culture the medium was passed through C₁₈‐SEP‐PAK cartridges in order to separate the cell exudates. The results show that Dunaliella salina influences the value of L_t but does not affect the value of K_s . The C₁₈SEP‐PAK retain only 50% of the ligands produced by the cells and capable of complexing copper.     

Characterization of fulvic acids during olive mill waste composting (Elemental,Thermal and fluorescence analyses)

Elemental analysis, fluorescence spectroscopy and differential scanning calorimetry (DSC) were applied to the study of fulvic acids isolated from different stages during olive mill waste composting. The fulvic extracted acids are characterized by a high nitrogen content and O/C ratio values that may result from the high degree of humification and the synthesis of more condensed humic complexes. This was confirmed by fluorescence spectroscopy in the synchronous-scan mode by the decrease of shoulder intensities at intermediate wavelengths indicating the increase of polycondensation and conjugation of unsaturated structures and the greater uniformity of fluorophores. Fluorescence spectra in the emission, excitation and synchronous modes became simpler with compost maturation. This was confirmed by DSC results which proved the high degree of polycondensation of aromatic nuclei of fulvic acid molecules during olive mill waste composting.     

Quantification of metallothionein in whole body gammarus locusta (crustacea: amphipoda) using differential pulse polarography

A polarographic method was optimised for the quantitative determination of metallothionein (MT) in whole body Gammarus locusta (Crustacea: Amphipoda). The identity of the MT-like proteins was examined using electrophoretic analysis (SDS-PAGE) and induction studies (water-borne exposures to copper). The MT-method was then used to examine changes in MT levels over the lifetime (juveniles, sub-adults and adults) of a laboratory population of G. locusta; copper (Cu) and zinc (Zn) body burden were also measured by flame atomic absorption spectrometry. MT was quantified by heat-denaturation of 30?000?g supernatants (to remove the bulk of non-MT proteins) followed by differential pulse polarography (DPP) to measure sulphydryl-group containing proteins. DPP proved to be a sensitive and reliable method to quantify heat-stable total sulphydryl-proteins. The majority of the latter was indicated to be MT from SDS-PAGE and induction studies. SDS-PAGE revealed a putative MT of 23?±?0.6?kDa app. mol. wt., consistent with the average size of dimeric MTs (10–20?kDa) found in several aquatic invertebrate species. Copper-exposure revealed parallel increases in the amounts of 23?kDa protein and total sulphydryl-proteins. Levels of whole body MT (rabbit pure MT as standard) range between 1.3 and 2.3?mg?g^?1 dry wt. over the lifetime of G. locusta. Sex-related changes in MT status were observed, the levels in females being 1.6 times higher than in males (p<0.05). Copper and Zn body content changed over the lifetime of G. locusta, the levels in juveniles (p>0.05) and sub-adults (p<0.05) being higher than in adults. It is concluded that the inclusion of MT in ecotoxicological studies with amphipod crustaceans require some caution with respect to the stages of moulting and/or sexual maturation of organisms, but this should not provide any major impediment in its use in metal pollution monitoring.     

Fish wars and cooperation maintenance

In this paper, a discrete-time game model related to a bioresource management problem (fish catching) is considered. We divide a fishery into regions, which are exploited by single players. The center (referee) shares a reservoir between the competitors. The players (countries), which harvest the fish stock are the participants of this game.We assume that there are migratory exchanges between the regions of the reservoir. Therefore, the stock in one region depends not only on the previous stock and catch in the region, but also on the stock and catch in neighboring regions. We derive the Nash and cooperative equilibria for an infinite planning horizon.We consider two ways to maintain the cooperation: incentive equilibrium and time-consistent imputation distribution procedure. We investigate the cooperative incentive equilibrium in the case when the center punishes players for a deviation.Also we consider the case when the center is a player and find the Shapley value and time-consistent imputation distribution procedure. We introduce a new condition which offers an incentive to players to keep cooperating.     

Use of thermal analysis techniques (TG-DSC) for the characterization of diverse organic municipal waste streams to predict biological stability prior to land application

The use of organic municipal wastes as soil amendments is an increasing practice that can divert significant amounts of waste from landfill, and provides a potential source of nutrients and organic matter to ameliorate degraded soils. Due to the high heterogeneity of organic municipal waste streams, it is difficult to rapidly and cost-effectively establish their suitability as soil amendments using a single method. Thermal analysis has been proposed as an evolving technique to assess the stability and composition of the organic matter present in these wastes. In this study, three different organic municipal waste streams (i.e., a municipal waste compost (MC), a composted sewage sludge (CS) and a thermally dried sewage sludge (TS)) were characterized using conventional and thermal methods. The conventional methods used to test organic matter stability included laboratory incubation with measurement of respired C, and spectroscopic methods to characterize chemical composition. Carbon mineralization was measured during a 90-day incubation, and samples before and after incubation were analyzed by chemical (elemental analysis) and spectroscopic (infrared and nuclear magnetic resonance) methods. Results were compared with those obtained by thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. Total amounts of CO₂ respired indicated that the organic matter in the TS was the least stable, while that in the CS was the most stable. This was confirmed by changes detected with the spectroscopic methods in the composition of the organic wastes due to C mineralization. Differences were especially pronounced for TS, which showed a remarkable loss of aliphatic and proteinaceous compounds during the incubation process. TG, and especially DSC analysis, clearly reflected these differences between the three organic wastes before and after the incubation. Furthermore, the calculated energy density, which represents the energy available per unit of organic matter, showed a strong correlation with cumulative respiration. Results obtained support the hypothesis of a potential link between the thermal and biological stability of the studied organic materials, and consequently the ability of thermal analysis to characterize the maturity of municipal organic wastes and composts.     

Population as an oscillating system

In this paper we present a new approach describing population dynamics based on the view of a population as an oscillating system. To develop a mathematical model of an oscillating population, we applied a third-order differential equation. Our model describes population dynamics within a parametric-temporal continuum, formed by the relative values of population growth and decrease over time. In this paper we also illustrate how our oscillative model effectively compliments the existing suite of models in population dynamics.