The Effect of CTBN Concentrations on the Kinetic Parameters of Decomposition of Blends of Epoxy Resins Modified with Carboxyl-Terminated Liquid Copolymer

Diglycidyl ether of bisphenol—A (DGEBA)—based epoxy resin was blended in the ratio of 3:1 (weight basis) with cycloaliphatic epoxy (CAE) resin. The prepared blend sample was further blended with different weight percentages of carboxyl-terminated butadiene acrylonitrile copolymer (CTBN) ranging between 0 and 25 wt% with an interval of 5 wt% and cured with stiochiometric amounts of 4, 4’- diamino diphenyl sulphone (DDS) cure agent. Structural changes during blending were studied by Fourier-transform infra-red (FTIR) spectroscopic analysis. The kinetic parameters, viz., order of decomposition reaction (n), activation energy (E), pre-exponential factor (Z) and rate decomposition constant (k), for the decomposition of the samples were calculated by applying Coats-Redfern equation over thermogravimetric (TG) data. The degradation of each sample followed second-order degradation kinetics, which was calculated by Coats-Redfern equation using best-fit analysis. This was further confirmed by linear regression analysis. The validity of data was checked by t-test statistical analysis. Further, the blend sample had higher initial degradation temperature and activation energy than its respective pure epoxy resin indicating that the CTBN acted as thermal stabilizer for epoxy resin which improved the thermal stability.     

Mechanisms of cross-shelf transport of crab megalopae inferred from a time series of daily abundance

From 20 July 1982 to 19 July 1984, crab megalopae were trapped daily from the Scripps Institution of Oceanography pier. Pachygrapsus crassipes, Portunus xantusii, Cancer spp., Hemigrapsus spp., and Majid crab megalopae dominated the catch. Yearly, seasonal, and daily variations in the magnitude of the catch were observed. Yearly and seasonal variations were probably due to a strong El Niño event that occurred during the study and to the timing of spawning and duration of the larval phase, respectively. Daily variation was correlated with oceanographic processes that can transport larvae to shore. Catch of some taxon during some seasons correlated with wind stress suggesting that transport was wind driven. The correlations were, however, weak and the sign of the correlation varied between years. The maximum daily tidal range was significantly correlated (cross-correlations and cross Fourier analysis) to both daily seawater temperature anomalies (surface and bottom) and daily catch of crab megalopae in all taxa enumerated. Significant correlations between tidal range and temperature anomalies suggest that temperature anomalies were primarily due to the shoreward transport of warm and cold water by the internal tides. The consistent and relatively strong relationship between tidal range and catch of megalopae (the cross-Fourier analysis suggests that from 20 to >90% of the variation in catch can be attributed to variation in the tidal range) suggest that much of the shoreward transport of megalopae was via the internal tides. Shoreward transport of larvae by internal tides may be due to internal cold bores or convergences over large tidally generated internal waves (solitons). Peak catches of megalopae, however, were often not associated with cold anomalies suggesting that transport was due to moving convergences over internal waves.     

Application of lead isotopic methods to the study of the anthropogenic lead provenance in Spanish overbank floodplain deposits

Changes in the principal sources of Pb in overbank sediment profiles have been documented for two Spanish areas by using Pb isotopes and Pb concentrations. These locations (Madrid and Tinto–Odiel basin) represent two of the most contaminated regions in Spain. The Community of Madrid is characterized by heavy industrial and urban activity, focused mainly in Madrid City. The Tinto–Odiel basin drains the Iberian Pyrite Belt, which hosts many polymetallic massive sulphides and is heavily affected by mining activities in their headwaters. It has been proven that the influence of anthropogenic activity is reflected in these overbank deposits by variations in Pb concentrations that, in general, correlate with shifts in the ²⁰⁶Pb/²⁰⁷Pb ratio. Rivas profile (downstream of Madrid) was found to be the most anthropogenically influenced site. The sediments within this profile which were recently deposited (170 ± 40 years BP) have the least radiogenic signatures. ²⁰⁶Pb/²⁰⁷Pb ratios ranged between 1.1763 and 1.1876 indicating significant contributions of anthropogenic Pb. In contrast, profiles upstream of Madrid possess an average ²⁰⁶Pb/²⁰⁷Pb ratio of 1.2272. It is difficult to clearly identify the most prominent source as the sediments appear to be characterized by an input from several sources. The floodplain profiles in the Tinto–Odiel basin exhibit uniform ²⁰⁶Pb/²⁰⁷Pb ratios ranging from 1.1627 (Odiel river) to 1.1665 (Tinto river). These ratios are similar to the ones possessed by sulphide ores in the area and differ from the ratios of other nonmineralized formations in the basin, indicating that mining activities are the primary, if not sole, source of Pb to the sediments.     

Characteristics of residual organochlorine pesticides in soils under different land-use types on a coastal plain of the Yellow River Delta

The residual levels of organochlorine pesticides (OCPs) were examined in soils covering five types of land use along a salinity gradient on the Yellow River Delta. The most prominent OCPs were dichlorodiphenyltrichloroethane (∑DDT, arithmetic mean = 5.11 μg kg^?1), hexachlorocyclohexane (∑HCH, 1.69 μg kg^?1) and ∑endosulfan (10.4 μg kg^?1). The spatial variability of OCPs composition shifted from γ-HCH and o,p′-DDT dominated pesticides in coastal soils to p,p′-DDE dominated pesticides in inland soils. In different land-use types, the percentages of β-HCH and p,p′-DDE are characterized by more recalcitrant components in decreasing order of vegetable fields, cereal fields, cotton fields, wetlands and tidal flats with increasing soil salinity. However, the less recalcitrant components, γ-HCH and o,p′-DDT, showed an opposite trend. Endosulfan sulfate predominated in all land-use types. Residual levels of β-HCH were affected by soil organic matter. The correlations between γ-HCH and clay content and between p,p′-DDE, o,p′-DDT and salinity might associate with the influence of sediment cotransport by the Yellow River and the density of anthropogenic activities in coastal region. Depth distribution of the OCPs in typical soil profiles also implied that local historical usage and sediment transport by the Yellow River both affected the OCPs residual in this region.     

Simulations of the flow in the Mahakam river–lake–delta system,Indonesia

Large rivers often present a river–lake–delta system, with a wide range of temporal and spatial scales of the flow due to the combined effects of human activities and various natural factors, e.g., river discharge, tides, climatic variability, droughts, floods. Numerical models that allow for simulating the flow in these river–lake–delta systems are essential to study them and predict their evolution under the impact of various forcings. This is because they provide information that cannot be easily measured with sufficient temporal and spatial detail. In this study, we combine one-dimensional sectional-averaged (1D) and two-dimensional depth-averaged (2D) models, in the framework of the finite element model SLIM, to simulate the flow in the Mahakam river–lake–delta system (Indonesia). The 1D model representing the Mahakam River and four tributaries is coupled to the 2D unstructured mesh model implemented on the Mahakam Delta, the adjacent Makassar Strait, and three lakes in the central part of the river catchment. Using observations of water elevation at five stations, the bottom friction for river and tributaries, lakes, delta, and adjacent coastal zone is calibrated. Next, the model is validated using another period of observations of water elevation, flow velocity, and water discharge at various stations. Several criteria are implemented to assess the quality of the simulations, and a good agreement between simulations and observations is achieved in both calibration and validation stages. Different aspects of the flow, i.e., the division of water at two bifurcations in the delta, the effects of the lakes on the flow in the lower part of the system, the area of tidal propagation, are also quantified and discussed.     

Bayesian analysis of Jolly-Seber type models

We propose the use of finite mixtures of continuous distributions in modelling the process by which new individuals, that arrive in groups, become part of a wildlife population. We demonstrate this approach using a data set of migrating semipalmated sandpipers (Calidris pussila) for which we extend existing stopover models to allow for individuals to have different behaviour in terms of their stopover duration at the site. We demonstrate the use of reversible jump MCMC methods to derive posterior distributions for the model parameters and the models, simultaneously. The algorithm moves between models with different numbers of arrival groups as well as between models with different numbers of behavioural groups. The approach is shown to provide new ecological insights about the stopover behaviour of semipalmated sandpipers but is generally applicable to any population in which animals arrive in groups and potentially exhibit heterogeneity in terms of one or more other processes.     

Sparse PCA and investigation of multi-elements compositional repositories: theory and applications

The geochemistry of floodplain sediments is fundamental to monitor environmental changes and to quantify their contribution to natural and anthropic processes. A floodplain sediment composition is a vector of positive elements which sum to a fixed constant. The analysis of high-dimensional compositions requires methods that produce results involving only a small portion of the original variables. On the other hand, the analysis must take into account the additional constraints specific to compositions. With the purpose of studying these problems, a new procedure for sparse PCA is proposed on European floodplain sediment samples.     

Photochemical indicators of ozone sensitivity: application in the Pearl River Delta,China

Surface O₃ production has a highly nonlinear relationship with its precursors. The spatial and temporal heterogeneity of O₃-NO _x -VOC-sensitivity regimes complicates the control-decision making. In this paper, the indicator method was used to establish the relationship between O₃ sensitivity and assessment indicators. Six popular ratios indicating ozone-precursor sensitivity, HCHO/NO _y , H₂O₂/ HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z , were evaluated based on the distribution of NO_x- and VOC-sensitive regimes. WRF-Chem was used to study a serious ozone episode in fall over the Pearl River Delta (PRD). It was found that the south-west of the PRD is characterized by a VOCsensitive regime, while its north-east is NO _x -sensitive, with a sharp transition area between the two regimes. All indicators produced good representations of the elevated ozone hours in the episode on 6 November 2009, with H₂O₂/HNO₃ being the best indicator. The threshold sensitivity levels for HCHO/NO_y, H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were estimated to be 0.41, 0.55, 10.2, 14.0, 19.1, and 0.38, respectively. Threshold intervals for the indicators H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were able to identify more than 95% of VOC- and NO _x -sensitive grids. The ozone episode on 16 November 16 2008 was used to independently verify the results, and it was found that only H₂O₂/HNO₃ and H₂O₂/NO _z were able to differentiate the ozone sensitivity regime well. Hence, these two ratios are suggested as the most appropriate indicators for identifying fall ozone sensitivity in the PRD. Since the species used for indicators have seasonal variation, the utility of those indicators for other seasons should be investigated in the future work.

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The selective advantage of host feminization: a case study of the green crab Carcinus maenas and the parasitic barnacle Sacculina carcini

Male crabs infected by parasitic barnacles (Rhizocephala) are known to be morphologically feminized. Here, we investigate morphological chances in green crabs, Carcinus maenas, induced by the parasitic barnacle Sacculina carcini. Infected males acquire a broader, longer and segmented abdomen, fringed with marginal setae. Copulatory appendages and pereopods are reduced in length, and the chelae become smaller. The feminization show great individual variation. Males with scars from lost externae, the parasites reproductive organ situated under the abdomen, are less modified than males carrying an externa, and the feminization is more pronounced in smaller than in larger males. No super-feminization is evident in female crabs that remain morphologically unaffected by infection. The protective value of a parasitically induced enlargement of the male abdomen may constitute an adaptation that increases parasite longevity. The additional effects on male morphology are viewed as pleiotropic side effects of the main adaptive value of enlarging the abdomen.     

Evolution, radiation and chemotaxonomy of Lamellodysidea, a demosponge genus with anti-plasmodial metabolites

Sponges of the family Dysideidae (Dictyoceratida) are renowned for their diversity of secondary metabolites, and its genus Lamellodysidea, particularly Lamellodysidea herbacea, is the most studied taxon biochemically. Despite its importance, the taxonomic status of L. herbacea—whether it is a distinct species or a species complex—has never been assessed. Recent biochemical profiling revealed anti-plasmodial activity of brominated compounds in Lamellodysidea of the Pacific. Here, we present a comparative chemotaxonomic and molecular analysis of selected Dysideidae from the Pacific and the Indian Ocean (New Caledonia, Great Barrier Reef, Fiji, Mayotte, Guam, Palau). We investigated the phylogenetic relationships between the populations and assessed their bioactive (PBDE) compounds in order to unravel the taxonomic status of this commercially important group of sponges and assessed patterns of dispersal and biochemical variation. The molecular phylogeny was based on the internal transcribed ribosomal spacer and compared against a PBDE phylogeny for several specimens. Molecular data revealed a diversity of Indo-Pacific L. herbacea populations, also reflected by different PBDE compound profiles. Molecular and biochemical data also revealed a Lamellodysidea species new to science. Several specimens misidentified as Lamellodysidea were detected based on their position on different clades in the molecular phylogeny and their production of different halogenated compounds (brominated vs. chlorinated). The direct comparison of molecular and biochemical data also provided evidence for the occurrence of a host switch event and support for the theory that abiotic factors, such as sedimentation, affect the chemical constituents produced in L. herbacea.