Kinetic degradation processes of butyl- and phenyltins in soils

The degradation of organotin compounds (OTC) in agricultural and forest soils is studied in sandy soil samples. Individual experiments involving the three butyl- and the three phenyltins were carried out during 90 d in controlled conditions (darkness, 28 degrees C, aerobic conditions, 13% moisture) and with spiking concentration representative of environmental levels (20-50 micrg(Sn) kg(-1)). After the validation of first-order degradation kinetic model, mechanisms involved throughout the study were considered. Degradation pathways are proposed for butyl- and phenyltins and discussed according to literature data. The degradation of mono- (MBT, MPhT), di-organotins (DBT, DPhT) and TBT is clearly identified as a single successive loss of an organic group whereas TPhT is directly degraded to MPhT. The half-life times were dependent on their substitution degree, ranging from 24 (TPhT) to 220 (MBT) d. The less substituted the OTC is, the more persistent it is. In the range 4.3-5.7, pH does not seem to influence OTC degradation under the present operating conditions. Finally this study shows the significant persistence in soil samples in our experimental conditions for most of studied organotins and highlights the potential impact on soil quality.     

Maternal provisioning for larvae and larval provisioning for juveniles in the toxopneustid sea urchin <Emphasis Type="Italic">Tripneustes gratilla</Emphasis>

Lipid and protein biochemistry of eggs (84 μm in diameter), embryos and early larvae of the tropical echinoid Tripneustes gratilla (Linnaeus 1758) were quantified to determine how maternal provisions are used to fuel development of the echinopluteus. The eggs contained a mean of 30.82 ng lipid and 87.32 ng protein. Energetic lipids were the major lipid component (55.52% of total lipid) with the major class being triglyceride (TG: mean 15.9 ng, 51.58% of total). Structural lipid was dominated by phospholipid (PL: mean 11.18 ng, 36.26% of total). Early embryogenesis was not a major drain on egg energetic lipid and protein. Development of the functional feeding larva used ca. 50% of initial egg energetic lipid and most of this was TG. Maternal TG was still present in the 8-day echinoplutei and it was estimated that this energetic lipid would be depleted in unfed larvae by day 10. There was no change in PL. In a separate experiment lipid biochemistry of rudiment stage larvae and early developing juveniles were quantified to determine how lipids are used during metamorphosis. Fed larvae accumulated lipid (mean 275.49 ng) with TG and PL being the major energetic and structural lipids, respectively. Larval lipid stores were not appreciably depleted by metamorphosis and so were available for the early benthic stage juvenile. Juveniles started their benthic existence with 314 ng total lipid (TG: mean 46.84 ng, 14.9% of total, PL: mean 137.51 ng, 43.67% of total). Nile Red histochemistry and histology showed that the stomach serves as a nutrient storage organ and, that lipid stores accrued by larvae sustain developing juveniles for up to 4 days post settlement. Triglyceride supported both non-feeding stages of development and the prefeeding larval and perimetamorphic benthic stage. In this first study of lipid stores in settlement stage echinoderm larvae, we show that T. gratilla larvae sequester the same major energetic lipid (TG) to support the early juvenile that the female parent provided them to fuel early development.     

Towards a framework for assessment and management of cumulative human impacts on marine food webs

Effective ecosystem‐based management requires understanding ecosystem responses to multiple human threats, rather than focusing on single threats. To understand ecosystem responses to anthropogenic threats holistically, it is necessary to know how threats affect different components within ecosystems and ultimately alter ecosystem functioning. We used a case study of a Mediterranean seagrass (Posidonia oceanica) food web and expert knowledge elicitation in an application of the initial steps of a framework for assessment of cumulative human impacts on food webs. We produced a conceptual seagrass food web model, determined the main trophic relationships, identified the main threats to the food web components, and assessed the components’ vulnerability to those threats. Some threats had high (e.g., coastal infrastructure) or low impacts (e.g., agricultural runoff) on all food web components, whereas others (e.g., introduced carnivores) had very different impacts on each component. Partitioning the ecosystem into its components enabled us to identify threats previously overlooked and to reevaluate the importance of threats commonly perceived as major. By incorporating this understanding of system vulnerability with data on changes in the state of each threat (e.g., decreasing domestic pollution and increasing fishing) into a food web model, managers may be better able to estimate and predict cumulative human impacts on ecosystems and to prioritize conservation actions.     

Two leaks detection in viscoelastic pipeline systems by means of transient

This paper presents a technique for detecting and locating leaks in a single viscoelastic pipe, by means of transient analysis. The system studied is a reservoir-pipe-valve structure. The viscoelastic behavior of the pipe wall material is modeled by a generalized KelvinVoigt model. To determine the leak location, the mathematical formulation has been solved by the method of characteristics. The approach by the method of characteristics is often chosen because it is based on the concept of acoustic wave propagation which is the main mechanism of all transient events considered. The presence of the two leaks in a pipe partially reflects pressure waves initiated by the sudden closure of a downstream shut-off valve. These waves affect the shape and the amplitude of the time-history-pressure. The computed results describe the influence of the presence of two leaks on pressure time-history and the effect of leaks locations and sizes on the pressure signal behavior. The effect of the pipe wall viscoelasticity on the two leaks detection and sizing is also discussed. The leaks discharges are determined by resolving two independent equations derived from literatures and based on transient analysis. The friction and leaks depths effects on two leaks locations and sizing are involved.     

MIE determination and thermal degradation study of PA12 polymer powder used for laser sintering

Pulverized materials such as metallic or polymer powders play a considerable role in many industrial processes. Their use requires the introduction of preventive safeguards to control the plant's safety.PA12 polymer powder processing by laser sintering is characteristic of this tendency. The present work concerns PA12 powder (bimodal particle size distribution: 10 μm and 55 μm) and relates to explosion sensitivity and the thermal degradation of this powder, which can occur during laser sintering. Minimum Ignition Energy is determined using a modified Hartmann tube combined with the Langlie method developed in the PRISME Laboratory. This study shows the influence of parameters such as distance between the electrodes, powder concentration and arc power on MIE values. Theses parameters vary in the range of 3–6 A for the current intensity of the spark and the electrode gap in the range of 2.5–4 mm. The MIE is obtained for a spark gap of 3 mm and current intensity of the 4 A spark in our device. It shows that the MIE is less than 40 mJ for concentrations approaching 1000 g/m³. At lower concentrations (under 150 g/m³) the MIE increases but discrepancies in measurements appear, probably because of the static electricity that creates strong irregularities in dust dispersion. The second part of this study concerns the thermal degradation of the PA12 which is performed by thermogravimetric experiments coupled with mass spectrometric (MS) analysis for gas investigation. The mass loss measurement combined with the gas analysis allows the principal stages of degradation to be determined so as to calculate the kinetics parameter PA12. Experiments have been performed for different heating rates between 1 and 30 K min^?1 and the reproducibility of experiments has been verified. The activation energy is determined using two methods: Freidman and KAS. For a reaction rate of between 0.2 and 0.6, the activation energy is nearly constant. The KAS method gives a value of E_a = 250 kJ mol^?1 and the Friedman method gives E_a = 300 kJ mol^?1. The gas analysis by MS shows that oxidation begins at over 350 °C and finishes at under 650 °C with the formation of CO₂ and H₂O. Other major peaks with an m/z ratio of 29, 28 and 30 are noticed in this range of temperature. They show the presence of intermediate species such as C₂H₆, NO or CH₂O. The presence of HCN is also detected (m/z ratio of 27).     

Diversity trends in Neogene European ungulates and rodents: large-scale comparisons and perspectives

The ungulate and rodent fossil records are often used independently to understand mammalian evolutionary history. Few studies have directly compared both records over long time periods and large geographic areas. Here, we compiled two datasets of European fossil localities containing rodents and/or ungulates over 20 My (Early Miocene–Early Pliocene) and processed the data with the same methodology. We counted the raw diversity and calculated a measure of evenness (Pielou’s index). After controlling for potential biases on diversity estimators, we identify the evenness index as a more reliable estimator bringing interesting insights into the way both mammal groups are structured by biotic or abiotic factors. In this study, we consider that an uneven distribution of the species richness among families, when only some families successfully diversify within the “continental-scale community”, represents a lower adaptability of this community to the environmental context. Pielou’s index is used to estimate this adaptability through time. The responses of ungulates and rodents to environmental changes are very divergent, especially facing the climatic changes known since the Middle Miocene. The general patterns suggest that rodent broad-scale assemblages are affected by all kinds of perturbations, even short biotic and abiotic events, but show a better adaptability when facing long-term abiotic changes. Unlike rodents, the ungulate assemblages show more stability in periods of relative environmental stability but show less adaptability to long-term climatic changes. Life-history traits of mammals can help explain patterns of diversity and biogeography at different spatial scales and may probably partly explain the opposite patterns evidenced here.     

Modeling of secondary treated wastewater disinfection by UV irradiation: Effects of suspended solids content

This work aimed to study UV-resistant strains of Pseudomonas aeruginosa, to propose a formulation of the kinetics of secondary treated wastewater disinfection and to underline the influence of suspended solids on the inactivation kinetics of these strains. Some investigations were carried out for the validation of some simulation models, from the simplest, the kinetics model of Chick-Watson reduced to first order, to rather complex models such as multi-kinetic and Collins-Selleck models. Results revealed that the involved processes of UV irradiation were too complex to be approached by a simplified formulation, even in the case of specific strains of microorganisms and the use of nearly constant UV radiation intensity. In fact, the application of Chick-Watson model in its original form is not representative of the kinetics of UV disinfection. Modification, taking into account the speed change during the disinfection process, has not significantly improved results. On the other hand, the application of Collins-Selleck model demonstrates that it was necessary to exceed a least dose of critical radiation to start the process of inactivation. To better explain the process of inactivation, we have assumed that the action of disinfectant on the survival of lonely microorganisms is faster than its action on suspended solids protected or agglomerated to each others. We can assume in this case the existence of two inactivation kinetics during the processes (parallel and independent) of the first-order. For this reason, the application of a new kinetic model by introducing a third factor reflecting the influence of suspended solids in water on disinfection kinetics appeared to be determinant for modeling UV inactivation of P. aeruginosa in secondary treated wastewater.     

Effects of 5-year application of municipal solid waste compost on the distribution and mobility of heavy metals in a Tunisian calcareous soil

It is obvious that the application of solid waste compost improves the soil fertility. These wastes, however, may also have some negative effects on the agricultural environment due to their metal content. This research aimed at evaluating the influence of Tunisian municipal solid waste compost and farmyard manure on some chemical properties and the distribution of heavy metals in a calcareous Tunisian soil (clayey–loamy soil). A field plot experiment, without vegetation, was installed since 1999 at the experimental farm of the Agronomic National Institute of Tunis (INAT) in the region of Mornag (20 km south of Tunis, Tunisia). During 5 years, the field received yearly the following treatments: 0, 40, 80 and 120 t/ha of municipal solid waste compost and 0, 40 and 120 t/ha of manure. The fractionation of heavy metals in the soil was evaluated after 5 years using a sequential extraction procedure. The application of the two amendments was found to increase the content of organic matter, the total nitrogen content and the electrical conductivity, whereas it slightly decreased the soil pH. The addition of manure did not have a significant effect on the accumulation of heavy metals in the soil, whereas compost application increased the total concentration of heavy metals in the soil. The distribution of heavy metals between the different fractions in untreated and treated soils showed the residual fraction to be dominant, followed by the fraction bound to Fe and Mn oxides. The amount of Cu bound to the organic fraction increased with the application rate, which is probably caused by the formation of organic complexes. For the other metals, the increase of the association with organic matter is very limited. The application of compost moreover increases the amount of Zn associated with Fe and Mn oxides. The “Mobility Factor (MF)” was quite low and did not change after the 5-year application of the two organic amendments. It always remained lower than 10%, although for Cd it amounted to 17%.     

Removal of phosphate ions from aqueous solution using Tunisian clays minerals and synthetic zeolite

Phosphate ions are usually considered to be responsible for the algal bloom in receiving water bodies and aesthetic problems in water. From the environmental point of view, the management of such contaminant and valuable resource is very important. The present work deals with the removal of phosphate ions from aqueous solutions using kaolinitic and smectic clay minerals and synthetic zeolite as adsorbent. The pH effect and adsorption kinetic were studied. It was found that phosphate could be efficiently removed at acidic pH (between 4 and 6) and the second order model of kinetics is more adopted for all samples. The isotherms of adsorption of phosphate ions by the two clays and the zeolite samples show that the zeolite has the highest rate of uptake (52.9 mg P/g). Equilibrium data were well fitted with Langmuir and Freundlich isotherm.