Metallocene ethylene-1-octene copolymers:influence of comonomer content on thermo-mechanical, rheological, and thermo-oxidative behaviours before and after melt processing in an internal mixer

The influence of the comonomer content in a series of metallocene-based ethylene-1-octene copolymers (m-LLDPE) on thermo-mechanical, rheological, and thermo-oxidative behaviours during melt processing were examined using a range of characterisation techniques. The amount of branching was calculated from 13C NMR and studies using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were employed to determine the effect of short chain branching (SCB, comonomer content) on thermal and mechanical characteristics of the polymer. The effect of melt processing at different temperatures on the thermo-oxidative behaviour of the polymers was investigated by examining the changes in rheological properties, using both melt flow and capillary rheometry, and the evolution of oxidation products during processing using infrared spectroscopy. The results show that the comonomer content and catalyst type greatly affect thermal, mechanical and oxidative behaviour of the polymers. For the metallocene polymer series, it was shown from both DSC and DMA that (i) crystallinity and melting temperatures decreased linearly with comonomer content, (ii) the intensity of the ß-transition increased, and (iii) the position of the tan δmax peak corresponding to the a-transition shifted to lower temperatures, with higher comonomer content. In contrast, a corresponding Ziegler polymer containing the same level of SCB as in one of the m-LLDPE polymers, showed different characteristics due to its more heterogeneous nature: higher elongational viscosity, and a double melting peak with broader intensity that occurred at higher temperature (from DSC endotherm) indicating a much broader short chain branch distribution. The thermo-oxidative behaviour of the polymers after melt processing was similarly influenced by the comonomer content. Rheological characteristics and changes in concentrations of carbonyl and the different unsaturated groups, particularly vinyl, vinylidene and trans-vinylene, during processing of m-LLDPE polymers, showed that polymers with lower levels of SCB gave rise to predominantly crosslinking reactions at all processing temperatures. By contrast, chain scission reactions at higher processing temperatures became more favoured in the higher comonomer-containing polymers. Compared to its metallocene analogue, the Ziegler polymer showed a much higher degree of crosslinking at all temperatures because of the high levels of vinyl unsaturation initially present.

Representing supply chain events on the Web of data

The Electronic Product Code Information Service (EPCIS) is an EPCglobal standard, that aims to bridge the gap between the physical world of RFID1 tagged artifacts, and information systems that enable their tracking and tracing via the Electronic Product Code (EPC). Central to the EPCIS data model are "events" that describe specific occurrences in the supply chain. EPCIS events, recorded and registered against EPC tagged artifacts, encapsulate the "what", "when", "where" and "why" of these artifacts as they flow through the supply chain. In this paper we propose an ontological model for representing EPCIS events on the Web of data. Our model provides a scalable approach for the representation, integration and sharing of EPCIS events as linked data via RESTful interfaces, thereby facilitating interoperability, collaboration and exchange of EPC related data across enterprises on a Web scale.

Short-term changes in phosphorus storage in an oligotrophic Everglades wetland ecosystem receiving experimental nutrient enrichment

Natural, unenriched Everglades wetlands are known to be limited by phosphorus (P) and responsive to P enrichment. However, whole-ecosystem evaluations of experimental P additions are rare in Everglades or other wetlands. We tested the response of the Everglades wetland ecosystem to continuous, low-level additions of P (0, 5, 15, and 30 μg L−1 above ambient) in replicate, 100 m flow-through flumes located in unenriched Everglades National Park. After the first six months of dosing, the concentration and standing stock of phosphorus increased in the surface water, periphyton, and flocculent detrital layer, but not in the soil or macrophytes. Of the ecosystem components measured, total P concentration increased the most in the floating periphyton mat (30 μg L−1: mean = 1916 μg P g−1, control: mean = 149 μg P g−1), while the flocculent detrital layer stored most of the accumulated P (30 μg L−1: mean = 1.732 g P m−2, control: mean = 0.769 g P m−2). Significant short-term responses of P concentration and standing stock were observed primarily in the high dose (30 μg L−1 above ambient) treatment. In addition, the biomass and estimated P standing stock of aquatic consumers increased in the 30 and 5 μg L−1 treatments. Alterations in P concentration and standing stock occurred only at the upstream ends of the flumes nearest to the point source of added nutrient. The total amount of P stored by the ecosystem within the flume increased with P dosing, although the ecosystem in the flumes retained only a small proportion of the P added over the first six months. These results indicate that oligotrophic Everglades wetlands respond rapidly to short-term, low-level P enrichment, and the initial response is most noticeable in the periphyton and flocculent detrital layer.

Cascading ecological effects of low-level phosphorus enrichment in the Florida Everglades

Few studies have examined long-term ecological effects of sustained low-level nutrient enhancement on wetland biota. To determine sustained effects of phosphorus (P) addition on Everglades marshes we added P at low levels (5, 15, and 30 µg L-1 above ambient) for 5 yr to triplicate 100-m flow-through channels in pristine marsh. A cascade of ecological responses occurred in similar sequence among treatments. Although the rate of change increased with dosing level, treatments converged to similar enriched endpoints, characterized most notably by a doubling of plant biomass and elimination of native, calcareous periphyton mats. The full sequence of biological changes occurred without an increase in water total P concentration, which remained near ambient levels until Year 5. This study indicates that Everglades marshes have a near-zero assimilative capacity for P without a state change, that ecosystem responses to enrichment accumulate over time, and that downstream P transport mainly occurs through biota rather than the water column.

Testing the Efficacy of Panax ginseng Extract as a Novel Anti-Quorum Sensing Agent

Quorum sensing (QS) is the phenomenon by which microorganisms regulate gene expression in response to cell-population density. These microorganisms synthesize and secrete small molecules known as autoinducers that increase in concentration as a function of cell density. Once the cell detects the minimal threshold concentration of an autoinducer, the gene expression is altered accordingly. Although the cellular circuitry responding to QS is relatively conserved, the cellular processes regulated by QS, for example are conjugation, motility, sporulation, biofilm formation and production of virulence factors importamt for infection. Since many pathogens have developed resistance to available antibiotics, novel therapies are required to further treat these pathogens. Inhibitors of QS are potential therapeutic candidates since they would inhibit virulence without selecting for antibiotic resistant strains. Previous studies have shown that the Chinese herb Panax ginseng contains compounds that inhibit QS activity. To further characterize this activity, a highly sensitive quantitative liquid assay was developed using a Chromobacterium violaceum AHL mutant, CV026 as a biomonitor strain. After confirmation that P. ginseng aqueous extracts had anti-QS activity, the extract was fractionated on a reverse phase C18 Sep Pak column. Most anti-QS activity was present in the flow through, and compounds eluted with ten percent acetonitrile in water antibacterial activity. We thus conclude that P. ginseng has anti-QS activity and the active compound is water soluble. Compounds from P. ginseng, could be used as a lead structure to design compound with higher anti-QS activity for therapeutic treatments.

Novel methodology for in situ carbon dioxide enrichment of benthic ecosystems

Future climate change will likely represent a major stress to shallow aquatic and coastal marine communities around the world. Most climate change research, particularly in regards to increased pCO2 and ocean acidification, relies on ex situ mesocosm experimentation, isolating target organisms from their environment. Such mesocosms allow for greater experimental control of some variables, but can often cause unrealistic changes in a variety of environmental factors, leading to “bottle effects.” Here we present an in situ technique of altering dissolved pCO2within nearshore benthic communities (e.g., macrophytes, algae, and/or corals) using submerged clear, open-top chambers. Our technique utilizes a flow-through design that replicates natural water flow conditions and minimizes caging effects. The clear, open-top design additionally ensures that adequate light reaches the benthic community. Our results show that CO2 concentrations and pH can be successfully manipulated for long durations within the open-top chambers, continuously replicating forecasts for the year 2100. Enriched chambers displayed an average 0.46 unit reduction in pH as compared with ambient chambers over a 6-month period. Additionally, CO2 and HCO3 – concentrations were all significantly higher within the enriched chambers. We discuss the advantages and disadvantages of this technique in comparison to other ex situ mesocosm designs used for climate change research.

Importance of storm events in controlling ecosystem structure and function in a Florida gulf coast estuary

From 8/95 to 2/01, we investigated the ecological effects of intra- and inter-annual variability in freshwater flow through Taylor Creek in southeastern Everglades National Park. Continuous monitoring and intensive sampling studies overlapped with an array of pulsed weather events that impacted physical, chemical, and biological attributes of this region. We quantified the effects of three events representing a range of characteristics (duration, amount of precipitation, storm intensity, wind direction) on the hydraulic connectivity, nutrient and sediment dynamics, and vegetation structure of the SE Everglades estuarine ecotone. These events included a strong winter storm in November 1996, Tropical Storm Harvey in September 1999, and Hurricane Irene in October 1999. Continuous hydrologic and daily water sample data were used to examine the effects of these events on the physical forcing and quality of water in Taylor Creek. A high resolution, flow-through sampling and mapping approach was used to characterize water quality in the adjacent bay. To understand the effects of these events on vegetation communities, we measured mangrove litter production and estimated seagrass cover in the bay at monthly intervals. We also quantified sediment deposition associated with Hurricane Irene's flood surge along the Buttonwood Ridge. These three events resulted in dramatic changes in surface water movement and chemistry in Taylor Creek and adjacent regions of Florida Bay as well as increased mangrove litterfall and flood surge scouring of seagrass beds. Up to 5 cm of bay-derived mud was deposited along the ridge adjacent to the creek in this single pulsed event. These short-term events can account for a substantial proportion of the annual flux of freshwater and materials between the mangrove zone and Florida Bay. Our findings shed light on the capacity of these storm events, especially when in succession, to have far reaching and long lasting effects on coastal ecosystems such as the estuarine ecotone of the SE Everglades.

Salinity and Chlorophyll a as Performance Measures to Rehabilitate a Mangrove-Dominated Deltaic Coastal Region: the Ciénaga Grande de Santa Marta–Pajarales Lagoon Complex, Colombia

Salinity, water temperature, and chlorophyll a (chl-a) biomass were used as performance measures in the period 1999–2001 to evaluate the effect of a hydrological rehabilitation project in the Ciénaga Grande de Santa Marta (CGSM)–Pajarales lagoon complex, Colombia where freshwater diversions were initiated in 1995 and completed in 1998. The objective of this study was to evaluate how diversions of freshwater into previously hypersaline (>80) environments changed the spatial and temporal distribution of environmental characteristics. Following the diversion, 19 surveys and transects using a flow-through system were surveyed in the CGSM–Pajarales complex to continuously measure selected water quality parameters. Geostatistical analysis indicates that hydrology and salinity regimes and water circulation patterns in the CGSM lagoon are largely controlled by freshwater discharge from the Fundacion, Aracataca, and Sevilla Rivers. Residence times in the CGSM lagoon were similar before (15.5 ± 3.8 days) and after (14.2 ± 2.0 days) the rehabilitation project and indicated that the system is flushed regularly. In contrast, chl-a biomass was highly variable in the CGSM–Pajarales lagoon complex and not related to discharge patterns. Mean annual chl-a biomass (44–250 μg L−1) following the diversion project was similar to values recorded since the 1980s and still remains among the highest reported in coastal systems around the world owing to its unique hydrology regulated by the Magdalena River and Sierra Nevada de Santa Marta watersheds and the high teleconnection to the El Niño Southern Oscillation (ENSO). Our results confirm that the reduction in salinity in the CGSM lagoon and Pajarales complex during 1999–2000 was largely driven by high precipitation (2500 mm) induced by the ENSO–La Niña rather than by the freshwater diversions.

Geochemical determination of the fate and transport of injected fresh wastewater to a deep saline aquifer

Deep well injection into non-potable saline aquifers of treated domestic wastewater has been used in Florida for decades as a safe and effective alternative to ocean outfall disposal. The objectives of this study were to determine the fate and transport of injected wastewater at two deep well injection sites in Miami Dade County, Florida, USA. Detection of ammonium in the Middle Confining units of the Floridan aquifer above the injection zone at both sites has been interpreted as evidence of upward migration of injected wastewater, posing a risk to underground sources of drinking water. Historical water quality data, including ammonia, chloride, temperature, and pH from existing monitoring wells at both sites from 1983 to 2008, major ions collected monthly from 2006 and 2008, and a synoptic sampling event for stable isotopes, tritium, and dissolved gases in 2008, were used to determine the source of ammonium in groundwater and possible migration pathways. Geochemical modeling was used to determine possible effects of injected wastewater on native water and aquifer matrix geochemistry. Injected wastewater was determined to be the source of elevated ammonium concentrations above ambient water levels, based on the results of major ion concentrations, tritium, dissolved noble gases and 15N isotopes analyses. Various possible fluid migration pathways were identified at the sites. Data for the south site suggest buoyancy-driven vertical pathways to overlying aquifers bypassing the confining units, with little mixing of injected wastewater with native water as it migrated upward. Once it is introduced into an aquifer, the injectate appeared to migrate advectively with the regional groundwater flow. Geochemical modeling indicated that CO 2-enriched injected wastewater allowed for carbonate dissolution along the vertical pathways, enhancing permeability along these flowpaths. At the north site, diffusive upward flow through the confining units or offsite vertical pathways were determined to be possible, however no evidence was detected for any on-site confining unit bypass pathway. No evidence was observed at either site of injected wastewater migration to the Upper Floridan aquifer, which is used as a municipal water supply and for aquifer storage and recovery.

Characteristics of surface-water flows in the ridge and slough landscape of Everglades National Park: implications for particulate transport

Over the last one hundred years, compartmentalization and water management activities have reduced water flow to the ridge and slough landscape of the Everglades. As a result, the once corrugated landscape has become topographically and vegetationally uniform. The focus of this study was to quantify variation in surface flow in the ridge and slough landscape and to relate flow conditions to particulate transport and deposition. Over the 2002–2003 and 2003–2004 wet seasons, surface velocities and particulate accumulation were measured in upper Shark River Slough in Everglades National Park. Landscape characteristics such as elevation, plant density and biomass also were examined to determine their impact on flow characteristics and material transport. The results of this study demonstrate that the release of water during the wet season not only increases water levels, but also increased flow speeds and particulate transport and availability. Further, flow speeds were positively and significantly correlated with water level thereby enhancing particulate transport in sloughs relative to ridges especially during peak flow periods. Our results also indicate that the distribution of biomass in the water column, including floating plants and periphyton, affects velocity magnitude and shape of vertical profiles, especially in the sloughs where Utricularia spp. and periphyton mats are more abundant. Plot clearing experiments suggest that the presence of surface periphyton and Utricularia exert greater control over flow characteristics than the identity (i.e., sawgrass or spike rush) or density of emergent macrophytes, two parameters frequently incorporated into models describing flow through vegetated canopies. Based on these results, we suggest that future modeling efforts must take the presence of floating biomass, such as Utricularia, and presence of periphyton into consideration when describing particulate transport.

Short-term changes in phosphorus storage in an oligotrophic Everglades wetland ecosystem receiving experimental nutrient enrichment

Natural, unenriched Evergladeswetlands are known to be limited by phosphorus(P) and responsive to P enrichment. However,whole-ecosystem evaluations of experimental Padditions are rare in Everglades or otherwetlands. We tested the response of theEverglades wetland ecosystem to continuous,low-level additions of P (0, 5, 15, and30 μg L−1 above ambient) in replicate,100 m flow-through flumes located in unenrichedEverglades National Park. After the first sixmonths of dosing, the concentration andstanding stock of phosphorus increased in thesurface water, periphyton, and flocculentdetrital layer, but not in the soil or macrophytes. Of the ecosystem components measured, total P concentration increased the most in the floating periphyton mat (30 μg L−1: mean = 1916 μg P g−1, control: mean =149 μg P g−1), while the flocculentdetrital layer stored most of the accumulated P(30 μg L−1: mean = 1.732 g P m−2,control: mean = 0.769 g P m−2). Significant short-term responsesof P concentration and standing stock wereobserved primarily in the high dose (30 μgL−1 above ambient) treatment. Inaddition, the biomass and estimated P standingstock of aquatic consumers increased in the 30and 5 μg L−1 treatments. Alterationsin P concentration and standing stock occurredonly at the upstream ends of the flumes nearestto the point source of added nutrient. Thetotal amount of P stored by the ecosystemwithin the flume increased with P dosing,although the ecosystem in the flumes retainedonly a small proportion of the P added over thefirst six months. These results indicate thatoligotrophic Everglades wetlands respondrapidly to short-term, low-level P enrichment,and the initial response is most noticeable inthe periphyton and flocculent detrital layer.

Everglades Ridge, Slough, and Tree Island Mosaics: Year 2 Annual Report

Status and history of the Ridge-Slough Mosaic The Florida Everglades is a large subtropical wetland with diverse hydrologic, edaphic, and vegetative characteristics. Historically, a significant portion of this system was a slow moving river originating from the Kissimmee River floodplain, flowing into the vast but shallow Lake Okeechobee, and draining south-southwest over extensive peatlands into Florida Bay (McVoy 2011). Human-induced alterations to the hydrologic regime, including reduction, stabilization, and impoundment of water flow through diversion and compartmentalization of water via canals and levees have degraded pre-drainage vegetation patterns and microtopographic structure (Davis and Ogden 1994, Ogden 2005, McVoy 2011). The Everglades peatland emerged 5,000 years ago with the stabilization of sea level at approximately current elevations (Loveless 1959, Gleason and Stone 1994). This, combined with subtropical rainfalls, allowed a vast mass of water to slowly flow over a limestone bedrock platform 160 km long and 50 km wide at a near uniform descent totaling about 6 m, ultimately reaching Florida Bay (Stephens 1956, Gleason and Stone 1994, McVoy 2011). Vegetation quickly colonized the area, and peat, in the absence of adequate respiration, accumulated on the limestone bedrock to a depth of 3-3.7 m (Gleason and Stone 1994, McVoy et al. 2011). The “River of Grass” referenced by Douglas (1947) alludes to the dually intertwined processes of the historic riverine nature of the Everglades and the vast sawgrass (Cladium jamaicense) communities that have dominated the landscape for about the last 1,000 years (Bernhardt and Willard 2009).

Investigation of spatial patterns of ground-water exchange with lakes, using a three-dimensional numerical model

Hydrogeologic variables controlling groundwater exchange with inflow and flow-through lakes were simulated using a three-dimensional numerical model (MODFLOW) to investigate and quantify spatial patterns of lake bed seepage and hydraulic head distributions in the porous medium surrounding the lakes. Also, the total annual inflow and outflow were calculated as a percentage of lake volume for flow-through lake simulations. The general exponential decline of seepage rates with distance offshore was best demonstrated at lower anisotropy ratio (i.e., Kh/Kv = 1, 10), with increasing deviation from the exponential pattern as anisotropy was increased to 100 and 1000. 2-D vertical section models constructed for comparison with 3-D models showed that groundwater heads and seepages were higher in 3-D simulations. Addition of low conductivity lake sediments decreased seepage rates nearshore and increased seepage rates offshore in inflow lakes, and increased the area of groundwater inseepage on the beds of flow-through lakes. Introduction of heterogeneity into the medium decreased the water table and seepage ratesnearshore, and increased seepage rates offshore in inflow lakes. A laterally restricted aquifer located at the downgradient side of the flow-through lake increased the area of outseepage. Recharge rate, lake depth and lake bed slope had relatively little effect on the spatial patterns of seepage rates and groundwater exchange with lakes.

Avaliação da influência de cinza da casca de arroz em cimentos para poços de petróleo submetidos à injeção de vapor

Reservoirs that present highly viscous oils require methods to aid in their recovery to the surface. The elev ated oil viscosity hinders its flow through porous media and conventional recovery methods have not obtained significant efficiency. As such, the injection of steam into the reservoir through an injection well has been the most widely used method of therma l recovery, for it allows elevated volumes of recovery due to the viscosity reduction of the oil, facilitating the oil’s mobility within the rock formation and consequently into the production well where it will be exploited. On the other hand, the injecti on of vapor not only affects the fluids found in the rock pores, but the entire structure that composes the well where it is injected due to the high temperatures used in the process. This temperature increment is conducted to the cement, found in the annu lus, responsible for the isolation of the well and the well casing. Temperatures above 110 ̊C create new fazes rich in calcium in the cement matrix, resulting in the reduction of its permeability and the consequential phenomenon of mechanical resistance ret rogression. These alterations generate faults in the cement, reducing the well’s hydraulic isolation, creating insecurity in the operations in which the well will be submitted as well as the reduction of its economic life span. As a way of reducing this re trograde effect, this study has the objective of evaluating the incorporation of rice husk ash as a mineral additive substitute of silica flour , commercially utilized as a source of silica to reduce the CaO/SiO 2 ratio in the cement pastes submitted to high temperatures in thermal recovery. Cement pastes were formulated containing 20 and 30% levels of ash, apart from the basic paste (water + cement) and a reference paste (water + cement + 40% silica flour) for comparison purposes. The tests were executed th rough compression resistance tests, X - Ray diffraction (XRD) techniques, thermogravimetry (TG), scanning electron microscopy (SEM) and chemical anal ysis BY X - ray fluorescence (EDS) on the pastes submitted to cure at low temperatures (45 ̊C) for 28 days following a cure at 280 ̊C and a pressure of 2,000 PSI for 3 days, simulating vapor injection. The results obtained show that the paste containing 30% r ice shell ash is satisfactory, obtaining mechanical resistance desired and equivalent to that of the paste containing 40% silica flour, since the products obtained were hydrated with low CaO/SiO 2 ratio, like the Tobermorita and Xonotlita fases, proving its applicability in well subject to vapor injection.

Estudo experimental sobre o comportamento do escoamento bifásico água - ar para a medição de vazão em placa de orifício

The measurement of flow through the prediction of differential pressure is widely used in industrial day-to-day, this happens mainly due to the fact that it is used for various types of fluids, such as gas flow and liquid with viscosity distinct even flow of fluids with particles in suspension. The suitability of this equipment for measuring mass flow in two-phase flow is of paramount importance for technological development and reliability of results. When it comes to two-phase flow the relationship between the fluids and their interactions are of paramount importance in predicting the flow. In this paper, we propose the use of concentric orifice plate used in small diameter pipes of 25.4 mm order where a two-phase flow flows between water-air. The measurement of single-phase flow was made with the use of data in NBR 5167-1 which was used to Stolz equation for measuring discharge coefficient. In the two-phase flow was used two correlations widely used in the prognosis of mass flow, the pattern of Zhang (1992) and the model of Chisholm (1967), to the homogeneous flow model. It was observed that the behavior found in Zhang model are consistent more realistic way the mass flow of two-phase flow, since the model Chisholm extrapolate the parameters for the downstream pressure P2, the orifice plate, and the rated discharge coefficient. The use of the change in pressure drop P1-P2 and discharge coefficient, led to a better convergence of the values obtained for the two-phase air-water stream.