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.     

Failure rate evaluation with influencing factors

A new methodology for failure rate evaluation with influencing factors is proposed. A quantitative part allows integrating potential available data from feedback. Then, a qualitative analysis deals with influencing factors such as design, environment, and use to provide more coherent and argued results. The main idea is to use some criteria to fix the failure rate within a prior interval, according to the influencing factor states. To this end, the system is broken up into main component groups. When a component group is susceptible to an influencing factor, its baseline failure rate is multiplied by the relevant influencing coefficient. A seven-step methodology is presented to define the model, identify and rate the influencing factors, set indicator functions taking the uncertainties into account, and calculate the influencing coefficients. The proposed methodology is global enough to be usable for a large number of safety instrumented systems and influencing factors. For example, an application regarding safety pressure relief valves is given. The prospect is for more efficient risk management by acting both on systems and influencing factors.     

Modelling periphyton in irrigation canals

Periphyton developments in water distribution canals induce major disturbances for system management, such as clogging problems when fixed algae are detached. Periphyton models can be used to simulate and improve canal management. The purpose of this paper is to review the periphyton models which integrate a hydrodynamic effect, and to discuss their relevance for application in open-channels. Afterwards, a new model of periphyton detachment that integrates the hydrodynamic factor is proposed. An experiment in semi-real conditions is performed to compare periphyton development under four different hydrodynamic regimes. The proposed model is compared on experimental results with two existing models. The new model reproduces well the periphyton dynamics in the four canals simultaneously.     

Denitrification enzyme activity of fringe salt marshes in New England (USA)

Coastal salt marshes are a buffer between the uplands and adjacent coastal waters in New England (USA). With increasing N loads from developed watersheds, salt marshes could play an important role in the water quality maintenance of coastal waters. In this study we examined seasonal relationships between denitrification enzyme activity (DEA) in salt marshes of Narragansett Bay, Rhode Island, and watershed N loadings, land use, and terrestrial hydric soils. In a manipulative experiment, the effect of nutrient enrichment on DEA was examined in a saltmeadow cordgrass [Spartina patens (Aiton) Muhl.] marsh. In the high marsh, DEA significantly (p < 0.05) increased with watershed N loadings and decreased with the percent of hydric soils in a 200-m terrestrial buffer. In the low marsh, we found no significant relationships between DEA and watershed N loadings, residential land development, or terrestrial hydric soils. In the manipulation experiment, we measured increased DEA in N-amended treatments, but no effect in the P-amended treatments. The positive relationships between N loading and high marsh DEA support the hypothesis that salt marshes may be important buffers between the terrestrial landscape and estuaries, preventing the movement of land-derived N into coastal waters. The negative relationships between marsh DEA and the percent of hydric soils in the adjacent watershed illustrate the importance of natural buffers within the terrestrial landscape. Denitrification enzyme activity appears to be a useful index for comparing relative N exposure and the potential denitrification activity of coastal salt marshes.     

Secondary sexual characters and female quality in primates

Honest advertisement models of sexual selection propose that exaggerated secondary sexual ornaments are condition-dependent, and that only individuals with superior disease resistance will be able to express costly ornamentation. Studies of secondary sexual ornamentation and their maintenance by sexual selection tend to focus on males. However, females may also possess showy ornaments. We investigated whether female ornaments, in the form of sexual swellings, reliably signal female fitness in a semifree-ranging colony of mandrills (Mandrillus sphinx) at the Centre International de Recherches Médicales, Franceville (CIRMF), Gabon. We measured swelling height and width using photographs of periovulatory females over three mating seasons and compared swelling size with parasitism (using fecal analysis over one annual cycle), immune status (ratio of lymphocytes to neutrophils in blood smears made during captures), and genetic diversity (microsatellite heterozygosity). Swelling size varied by up to 10% between cycles in individual females, giving some support to the hypothesis that size differences may indicate the quality of individual swelling cycles. However, there was no significant difference in swelling size between conceptive and nonconceptive cycles. Measures of swelling size varied more between females than within females across swelling cycles, implying that swelling size was a relatively consistent characteristic of individual females. Swelling size was not significantly related to either general measures of parasitism and immune status, or to the closest available measures to each swelling cycle. Nor was swelling size significantly related to genetic diversity. The healthy, provisioned nature of the colony and problems associated with observational, correlational studies restrict interpretation of our data. However, in combination with previous findings that females of higher reproductive success do not show larger swellings, and that males do not allocate mating effort as a function of swelling size, these results imply that sexual swelling size does not indicate female quality in these semifree-ranging mandrills.     

Thermal hazard analysis of triacetone triperoxide (TATP) by DSC and GC/MS

Thermal degradation of triacetone triperoxide (TATP) was studied using differential scanning calorimetry (DSC) and gas chromatography/mass spectrometry (GC/MS). TATP, a potential explosive material, is powerful organic peroxide (OP) that can be synthesized by available chemicals, such as acetone and hydrogen peroxide in the laboratory or industries. The thermokinetic parameters, such as exothermic onset temperature (T₀) and heat of decomposition (ΔH_d), were determined by DSC tests. The gas products from thermal degradation of TATP were identified using GC/MS technique.In this study, H₂O₂ was mixed with propanone (acetone) and H₂SO₄ catalysis that produced TATP. The T₀ of TATP was determined to be 40 °C and E_a was calculated to be 65 kJ/mol. A thermal decomposition peak of H₂O₂ was analyzed by DSC and two thermal decomposition peaks of H₂O₂/propanone were determined. Therefore, H₂O₂/propanone mixture was applied to mix acid that was discovered a thermal decomposition peak (as TATP) in this study. According to risk assessment and analysis methodologies, risk assessment of TATP for the environmental and human safety issue was evaluated as 2-level of hazard probability rating (P) and 6-level of severity of consequences ratings (S). Therefore, the result of risk assessment is 12-point and was evaluated as “Undesirable” that should be enforced the effect of control method to reduce the risk.     

Effects of Habitat Disturbance from Residential Development on Breeding Bird Communities in Riparian Corridors

This study assessed the relationship among land use, riparian vegetation, and avian populations at two spatial scales. Our objective was to compare the vegetated habitat in riparian corridors with breeding bird guilds in eight Rhode Island subwatersheds along a range of increasing residential land use. Riparian habitats were characterized with fine-scale techniques (used field transects to measure riparian vegetation structure and plant species richness) at the reach spatial scale, and with coarse-scale landscape techniques (a Geographic Information System to document land-cover attributes) at the subwatershed scale. Bird surveys were conducted in the riparian zone, and the observed bird species were separated into guilds based on tolerance to human disturbance, habitat preference, foraging type, and diet preference. Bird guilds were correlated with riparian vegetation metrics, percent impervious surface, and percent residential land use, revealing patterns of breeding bird distribution. The number of intolerant species predominated below 12% residential development and 3% impervious surface, whereas tolerant species predominated above these levels. Habitat guilds of edge, forest, and wetland bird species correlated with riparian vegetation. This study showed that the application of avian guilds at both stream reach and subwatershed scales offers a comprehensive assessment of effects from disturbed habitat, but that the subwatershed scale is a more efficient method of evaluation for environmental management.     

Assessing the wildlife habitat value of New England salt marshes: I. Model and application

We developed an assessment model to quantify the wildlife habitat value of New England salt marshes based on marsh characteristics and the presence of habitat types that influence habitat use by terrestrial wildlife. Applying the model to 12 salt marshes located in Narragansett Bay, RI resulted in assessment scores that ranged over a factor of 1.5 from lowest to highest. Pre-classifying the results based on marsh size and morphology helped to compare assessment scores between marshes, and demonstrated that even the lower ranking marshes had substantial habitat value. Stepwise multiple regression analysis of assessment scores and model components demonstrated that salt marsh morphology, the degree of anthropogenic modification, and salt marsh vegetative heterogeneity were significant variables and accounted for 91.3% of the variability in component scores. Our results suggest that targeting these components for restoration may lead to improved assessment scores for our study marshes. We also examined the use of lower resolution remote sensing data in the assessment in order to minimize the time and effort required to complete the model. Scores obtained using smaller-scale, lower resolution data were significantly lower than those obtained using larger-scale, higher resolution data (df = 11; t = 2.2; p < 0.001). The difference was significantly positively correlated with the portion of the assessment score that could be attributed to trees, pools, and pannes and marsh size (r (2) =0.50, F = 4.6, p = 0.04), and could indicate a bias against smaller, more heterogeneous marshes. We conclude that potential differences need to be weighed against the time benefit of using this type of data, bearing in mind the marsh size and the goals of the assessment. Overall, our assessment can provide information to aid in prioritizing marshes for protection and restoration, identify marshes that may harbor significant biodiversity, or help monitor changes in habitat value over time.