910 resultados para hydraulic residence time
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Increasing nitrate concentrations in ground water is deleterious to human health as ingestion of such water can cause methemoglobinemia in infants and even cancer in adults (desirable limit for nitrate as NO3 - 45 mg/L, IS code 10500-1991). Excess nitrate concentrations in ground water is contributed by reason being disposal of sewage and excessive use of fertilizers. Though numerous technologies such as reverse osmosis, ion exchange, electro-dialysis, permeable reactive barriers using zerovalent iron etc exists, nitrate removal continues to be one of challenging issue as nitrate ion is highly mobile within the soil strata. The tapping the denitrification potential of soil denitrifiers which are inherently available in the soil matrix is the most sustainable approach to mitigate accumulation of nitrate in ground water. The insitu denitrification of sand and bentonite enhanced sand (bentonite content = 5%) in presence of easily assimilable organic carbon such as ethanol was studied. Batch studies showed that nitrate reduction by sand follows first order kinetics with a rate constant 5.3x10(-2) hr(-1) and rate constant 4.3 x 10(-2) hr(-1) was obtained for bentonite-enhanced sand (BS) at 25 degrees C. Filter columns (height = 5 cm and diameter = 8.2 cm) were constructed using sand and bentonite-enhanced sand as filter media. The filtration rate through both the filter columns was maintained at average value of 2.60 cm/h. The nitrate removal rates through both the filter media was assessed for solution containing 22.6 mg NO3-N/L concentrations while keeping C/N mass ratio as 3. For sand filter column, the nitrate removal efficiency reached the average value of 97.6% after passing 50 pore volumes of the nitrate solution. For bentonite-enhanced sand filter column, the average nitrate removal efficiency was 83.5%. The time required for effective operation for sand filter bed was 100 hours, while bentonite-enhanced sand filter bed did not require any maturation period as that of sand filter bed for effective performance because the presence of micropores in bentonite increases the hydraulic retention time of the solution inside the filter bed.
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In recent years, silver nanoparticles (AgNPs) have attracted significant attention owing to their unique physicochemical, optical, conductive and antimicrobial properties. One of the properties of AgNPs which is crucial for all applications is their stability. In the present study we unravel a mechanism through which silver nanoparticles are rendered ultrastable in an aqueous solution in complex with the protein ubiquitin (Ubq). This involves a dynamic and reversible association and dissociation of ubiquitin from the surface of AgNP. The exchange occurs at a rate much greater than 25 s(-1) implying a residence time of <40 ms for the protein. The AgNP-Ubq complex remains stable for months due to steric stabilization over a wide pH range compared to unconjugated AgNPs. NMR studies reveal that the protein molecules bind reversibly to AgNP with an approximate dissociation constant of 55 mu M and undergo fast exchange. At pH > 4 the positively charged surface of the protein comes in contact with the citrate capped AgNP surface. Further, NMR relaxation-based experiments suggest that in addition to the dynamic exchange, a conformational rearrangement of the protein takes place upon binding to AgNP. The ultrastability of the AgNP-Ubq complex was found to be useful for its anti-microbial activity, which allowed the recycling of this complex multiple times without the loss of stability. Altogether, the study provides new insights into the mechanism of protein-silver nanoparticle interactions and opens up new avenues for its application in a wide range of systems.
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We report molecular dynamics (MD) simulations to explore the influence of a counterion on the structure and dynamics of cationic and anionic solvation shells for various ions in methanol at 298 K. We show that the variation in ionic size of either the cation or the anion in an ion pair influences the solvation structure of the other ion as well as the diffusivity in an electrolyte solution of methanol. The extent of ionic association between the cation and its counteranion of different ionic sizes has been investigated by analyzing the radial distribution functions (RDFs) and the orientation of methanol molecules in the first solvation shell (FSS) of ions. It is shown that the methanol in the FSS of the anion as well the cation exhibit quite different radial and orientational structures as compared to methanol which lie in the FSS of either the anion or the cation but not both. We find that the coordination number (CN) of F-, Cr-, and I- ions decreases with increasing size of the anion which is contrary to the trend reported for the anions in H2O. The mean residence time (MRT) of methanol molecules in the FSS of ions has been calculated using the stable states picture (SSP) approach. It is seen that the ion-counterion interaction has a considerable influence on the MRT of methanol molecules in the FSS of ions. We also discuss the stability order of the ion-counterion using the potentials of mean force (PMFs) for ion pairs with ions of different sizes. The PMF plots reveal that the Li+-F- pair (small-small) is highly stable and the Li+-I- pair is least stable (small-large) in electrolyte solutions.
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Monthly population size of bait shrimp in the Bay was estimated from December 1984 to July 1985. Growth rates for male and female P. duorarum showed that pink shrimp exhibit a mean residence time in the nursery area (Biscayne Bay) of approximately 21 weeks. Monthly mortality rates were determined for each sex of pink shrimp. It was estimated that 23% and 26% of the male and female monthly population size, respectively, was absorbed by both the fishery and ecosystem monthly. Monthly proportion of the standing stock expected to die exclusively through fishing was 6.5% and 6.0% for males and females respectively. Estimates of emigration rates showed that approximately 4.0% of the population was lost from the Bay system each month. This surplus production was about 50% of the average monthly catch by the fleet. Fishing mortality represents only 8 - 9% of the losses to the shrimp population. The biggest source of loss is emigration, suggesting that most shrimp beyond the size at recruitment (to the fishery) are not utilized for food while in the Bay. Thus, it appears that the direct impact of the fishery on the bait shrimp population is relatively small. (PDF contains 46 pages)
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Seasonal variations in temperature, dissolved oxygen, and nutrients in the nearshore areas and in the canyon area of Monterey Bay, California during 1971-1972 were similar~ During upwelling periods, however, water in the nearshore areas was higher in temperature and oxygen and lower in nutrients than water in the canyon area~ This was caused by upwelled water moving north and south of the canyon into counterclockwise and clockwise flow in the northern and southern ends of the bay respectively. The water was heated by insolation and depleted of its nutrients by photosynthesis during this movement. The residence time of water in the nearshore northern and southern bay during upwelling is estimated to be 3 to 8 days, and this fits well into the above circulation pattern and average measured current velocities of 10 to 15 cm/sec~ There is sorne evidence that this circulation pattern and the estimated residence time may be also valid for on-upwelling periods. Upwelling apparently occurred in Monterey Submarine Canyon at rates of 0.4 to 2.9 m/day and was stronger in 1971 than 1972. (PDF contains 107 pages)
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Folate-targeted poly[(p-nitrophenyl acrylate)-co-(N-isopropylacrylamide)] nanohydrogel (F-SubMG) was loaded with 5-fluorouracil (5-FU) to obtain low (16.3 +/- 1.9 mu g 5-FU/mg F-SubMG) and high (46.8 +/- 3.8 mu g 5-FU/mg F-SubMG) load 5-FU-loaded F-SubMGs. The complete in vitro drug release took place in 8 h. The cytotoxicity of unloaded F-SubMGs in MCF7 and HeLa cells was low; although it increased for high F-SubMG concentration. The administration of 10 mu M 5-FU by 5-FU-loaded F-SubMGs was effective on both cellular types. Cell uptake of F-SubMGs took place in both cell types, but it was higher in HeLa cells because they are folate receptor positive. After subcutaneous administration (28 mg 5-FU/kg b.w.) in Wistar rats, F-SubMGs were detected at the site of injection under the skin. Histological studies indicated that the F-SubMGs were surrounded by connective tissue, without any signs of rejections, even 60 days after injection. Pharmacokinetic study showed an increase in MRT (mean residence time) of 5-FU when the drug was administered by drug-loaded F-SubMGs.
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Catalytic cracking of China no. 3 aviation kerosene using a zeolite catalyst was investigated under supercritical conditions. A three-stage heating/cracking system was specially designed to be capable of heating 0.8 kg kerosene to a temperature of 1050 K and pressure of 7.0 MPa with maximum mass flow rate of 80 g/s. Sonic nozzles of different diameters were used to calibrate and monitor the mass flow rate of the cracked fuel mixture. With proper experiment arrangements, the mass flow rate per unit throat area of the cracked fuel mixture was found to well correlate with the extent of fuel conversion. The gaseous products obtained from fuel cracking under different conditions were also analyzed using gas chromatography. Composition analysis showed that the average molecular weight of the resulting gaseous products and the fuel mass conversion percentage were a strong function of the fuel temperature and were only slightly affected by the fuel pressure. The fuel conversion was also shown to depend on the fuel residence time in the reactor, as expected. Furthermore, the heat sink levels due to sensible heating and endothermic cracking were determined and compared at varying test conditions. It was found that at a fuel temperature of similar to 1050 K, the total heat sink reached similar to 3.4 MJ/kg, in which chemical heat sink accounted for similar to 1.5 MJ/kg.
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Thermal cracking of China No.3 aviation kerosene was studied experimentally and analytically under supercritical conditions relevant to regenerative cooling system for Mach-6 scramjet applications. A two-stage heated tube system with cracked products collection/analysis was used and it can achieve a fuel temperature range of 700-1100 K, a pressure range of 3.5-4.5 MPa and a residence time of approximately 0.5-1.3 s. Compositions of the cracked gaseous products and mass flow rate of the kerosene flow at varied temperatures and pressures were obtained experimentally. A one-step lumped model was developed with the cracked mixtures grouped into three categories: unreacted kerosene, gaseous products and residuals including liquid products and carbon deposits. Based on the model, fuel conversion on the mass basis, the reaction rate and the residence time were estimated as functions of temperature. Meanwhile, a sonic nozzle was used for the control of the mass flow rate of the cracked kerosene, and correlation of the mass flow rate gives a good agreement with the measurements.
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Isoprene (ISO),the most abundant non-methane VOC, is the major contributor to secondary organic aerosols (SOA) formation. The mechanisms involved in such transformation, however, are not fully understood. Current mechanisms, which are based on the oxidation of ISO in the gas-phase, underestimate SOA yields. The heightened awareness that ISO is only partially processed in the gas-phase has turned attention to heterogeneous processes as alternative pathways toward SOA.
During my research project, I investigated the photochemical oxidation of isoprene in bulk water. Below, I will report on the λ > 305 nm photolysis of H2O2 in dilute ISO solutions. This process yields C10H15OH species as primary products, whose formation both requires and is inhibited by O2. Several isomers of C10H15OH were resolved by reverse-phase high-performance liquid chromatography and detected as MH+ (m/z = 153) and MH+-18 (m/z = 135) signals by electrospray ionization mass spectrometry. This finding is consistent with the addition of ·OH to ISO, followed by HO-ISO· reactions with ISO (in competition with O2) leading to second generation HO(ISO)2· radicals that terminate as C10H15OH via β-H abstraction by O2.
It is not generally realized that chemistry on the surface of water cannot be deduced, extrapolated or translated to those in bulk gas and liquid phases. The water density drops a thousand-fold within a few Angstroms through the gas-liquid interfacial region and therefore hydrophobic VOCs such as ISO will likely remain in these relatively 'dry' interfacial water layers rather than proceed into bulk water. In previous experiments from our laboratory, it was found that gas-phase olefins can be protonated on the surface of pH < 4 water. This phenomenon increases the residence time of gases at the interface, an event that makes them increasingly susceptible to interaction with gaseous atmospheric oxidants such as ozone and hydroxyl radicals.
In order to test this hypothesis, I carried out experiments in which ISO(g) collides with the surface of aqueous microdroplets of various compositions. Herein I report that ISO(g) is oxidized into soluble species via Fenton chemistry on the surface of aqueous Fe(II)Cl2 solutions simultaneously exposed to H2O2(g). Monomer and oligomeric species (ISO)1-8H+ were detected via online electrospray ionization mass spectrometry (ESI-MS) on the surface of pH ~ 2 water, and were then oxidized into a suite of products whose combined yields exceed ~ 5% of (ISO)1-8H+. MS/MS analysis revealed that products mainly consisted of alcohols, ketones, epoxides and acids. Our experiments demonstrated that olefins in ambient air may be oxidized upon impact on the surface of Fe-containing aqueous acidic media, such as those of typical to tropospheric aerosols.
Related experiments involving the reaction of ISO(g) with ·OH radicals from the photolysis of dissolved H2O2 were also carried out to test the surface oxidation of ISO(g) by photolyzing H2O2(aq) at 266 nm at various pH. The products were analyzed via online electrospray ionization mass spectrometry. Similar to our Fenton experiments, we detected (ISO)1-7H+ at pH < 4, and new m/z+ = 271 and m/z- = 76 products at pH > 5.
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A pirólise rápida é um processo para conversão térmica de uma biomassa sólida em altos rendimentos de um produto líquido chamado de bio-óleo. Uma das alternativas para geração de um bio-óleo com menor teor de oxigênio é uso de catalisadores nos reatores de pirólise, ao invés de um inerte, num processo chamado de pirólise catalítica. O objetivo deste trabalho foi testar catalisadores comerciais, um ácido e outro básico, em uma unidade piloto de leito fluidizado circulante. O catalisador ácido utilizado foi o Ecat, proveniente de uma unidade industrial de craqueamento catalítico fluido (FCC), e como catalisador básico foi utilizado uma hidrotalcita. Os resultados foram comparados com testes utilizando um material inerte, no caso uma sílica. Uma unidade piloto de FCC do CENPES foi adaptada para realizar os testes de pirólise catalítica. Após fase de modificação e testes de condicionamento, foi comprovada a viabilidade na utilização da unidade piloto adaptada. Contudo, devido a limitações operacionais, maiores tempos de residência tiveram que ser aplicados no reator, configurando o processo como pirólise intermediária. Foram então realizados testes com os três materiais nas temperaturas de 450C e 550C. Os resultados mostraram que o aumento do tempo de residência dos vapores de pirólise teve um impacto significativo nos rendimentos dos produtos quando comparada com o perfil encontrado na literatura para pirólise rápida, pois devido ao incremento das reações secundárias, produziu maiores rendimentos de coque e água, e menores rendimentos de bio-óleo. O Ecat e a hidrotalcita se apresentaram mais efetivos em termos de desoxigenação. O primeiro apresentou maiores taxas de desoxigenação via desidratação e a hidrotalcita apresentou maior capacidade para descarboxilação. Contudo, o uso de Ecat e hidrotalcita não se mostrou adequado para uso em reatores de pirólise intermediária, pois acentuou ainda mais as reações secundárias, gerando um produto com alto teor de água e baixo teor de compostos orgânicos no bio-óleo, além de produzirem mais coque. À temperatura de 450C estes efeitos foram mais pronunciados. Em termos de caracterização química, a condição de pirólise intermediária apontou para a produção de bio-óleos com perfil fenólico, sendo a sílica o que proporcionou os melhores rendimentos, principalmente a temperatura de 550C, sendo superiores aos encontrados na literatura. Analisando as composições dos bio-óleos sob a ótica da produção de biocombustíveis, nenhum dos materiais testados apresentou rendimentos consideráveis em hidrocarbonetos. De maneira geral, a sílica foi o que proporcionou os melhores resultados em termos de rendimento e qualidade do bio-óleo. Sua menor área superficial e sua característica de inerte se mostraram mais adequados para o processo de pirólise intermediária, onde a contribuição das reações secundárias em fase gasosa é elevada em função do tempo de residência no reator
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Neste trabalho foi estudado o tratamento simultâneo por biofiltração de emissões de compostos orgânicos voláteis, COV e gás sulfídrico, H2S, em estações de tratamento de despejos industriais, de refinaria de petróleo, ETDI. A biofiltração dos gases emanados da EDTI mostrou ser uma técnica de alta eficiência, atingindo valores de 95 a 99 % para tratamento simultâneo de COV e H2S em concentrações de 1000 e 100 ppmv, respectivamente. Foram realizados testes em 95 dias consecutivos de operação, em uma planta piloto instalada na Superintendência da Industrialização do Xisto, SIX, em São Mateus do Sul, Paraná, de março a agosto de 2006. O biofiltro foi do tipo fluxo ascendente, com 3,77 m3 de leito orgânico, composto de turfa, carvão ativado, lascas de madeira, serragem brita fina além de outros componentes menores. Foi realizada inoculação biológica com lodo filtrado de estação de tratamento de esgoto sanitário. As vazões de gás aplicadas variaram de 85 a 407 m3/h, resultando em taxas de carga de massa de 11,86 a 193,03 g de COV/h.m3 de leito e tempos de residência de 24 segundos a 6,5 minutos, com tempo ótimo de 1,6 minutos. A capacidade máxima de remoção do sistema encontrada, nas condições testadas, foi de 15 g de COV/h. m3, compatível com os valores encontrados na literatura para depuração biológica de COV na escala praticada. Também foi verificada a redução de componentes específicos de BTX, demonstrando boa degradabilidade dos compostos orgânicos. Finalmente o biofiltro demonstrou boa robustez biológica diante dos desvios operacionais intencionalmente provocados, tais como falta de umidade do leito, baixa temperatura, alta vazão, falta de carga de COV e baixo pH do leito. Depois de retomada a condição de operação estável, a biofiltração rapidamente atingiu o estado de equilíbrio, assegurando o uso eficiente e confiável da técnica no tratamento de gases de EDTI na indústria do hidrocarbonetos ou em refinarias de petróleo.
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We monitored the movements of 45 adult Summer Flounder (Paralichthys dentatus) between June 2007 and July 2008 through the use of passive acoustic telemetry to elucidate migratory and within-estuary behaviors in a lagoon system of the southern mid-Atlantic Bight. Between 8 June and 10 October 2007, fish resided primarily in the deeper (>3 m) regions of the system and exhibited low levels of large-scale (100s of meters) activity. Mean residence time within this estuarine lagoon system was conservatively estimated to be 130 days (range: 18–223 days), which is 1.5 times longer than the residence time previously reported for Summer Flounder in a similar estuarine habitat ~250 km to the north. The majority of fish remained within the lagoon system until mid-October, although some fish dispersed earlier and some of them appeared to disperse temporarily (i.e., exited the system for at least 14 consecutive days before returning). Larger fish were more likely to disperse before mid-October than smaller fish and may have moved to other estuaries or the inner continental shelf. Fish that dispersed after mid-October were more likely to return to the lagoon system the following spring than were fish that dispersed before mid-October. In 2008, fish returned to the system between 7 February and 7 April. Dispersals and returns most closely followed seasonal changes in mean water temperature, but photoperiod and other factors also may have played a role in large-scale movements of Summer Flounder.
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Serial, cyclonic, mesoscale eddies arise just north of the Charleston Bump, a topographical rise on the continental slope and Blake Plateau, and characterize the U.S. outer shelf and upper slope in the region of the Charleston Gyre. This region was transected during the winters of 2000, 2001, and 2002, and hydrographic data and larval fishes were collected. The hydrodynamics of the cyclonic eddies of the Charleston Gyre shape the distribution of larval fishes by mixing larvae from the outer continental shelf and the Gulf Stream and entraining them into the eddy circulation at the peripheral margins, the wrap-around filaments. Over all years and transects (those that intercepted eddies and those that did not), chlorophyll a concentrations, zooplankton displacement volumes, and larval fish concentrations were positively correlated. Chlorophyll a concentrations were highest in filaments that wrapped around eddies, and zooplankton displacement volumes were highest in the continental shelf–Gulf Stream–frontal mix. Overall, the concentration of all larval fishes declined from inshore to offshore with highest concentrations occurring over the outer shelf. Collections produced larvae from 91 fish families representing continental shelf and oceanic species. The larvae of shelf-spawned fishes—Atlantic Menhaden Brevoortia tyrannus, Round Herring Etrumeus teres, Spot Leiostomus xanthurus, and Atlantic Croaker Micropogonias undulatus—were most concentrated over the outer shelf and in the continental shelf–Gulf Stream–frontal mix. The larvae of ocean-spawned fishes—lanternfishes, bristlemouths, and lightfishes—were more evenly dispersed in low concentrations across the outer shelf and upper slope, the highest typically in the Gulf Stream and Sargasso Sea, except for lightfishes that were highest in the continental shelf–Gulf Stream–frontal mix. Detrended correspondence analysis rendered groups of larval fishes that corresponded with a gradient between the continental shelf and Gulf Stream and Sargasso Sea. Eddies propagate northeastward with a residence time on the outer shelf and upper slope of ∼1 month, the same duration as the larval period of most fishes. The pelagic habitat afforded by eddies and fronts of the Charleston Gyre region can be exploited as nursery areas for feeding and growth of larval fishes within the southeastern Atlantic continental shelf ecosystem of the U.S. Eddies, and the nursery habitat they provide, translocate larvae northeastward.
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We measured growth and movements of individually marked free-ranging juvenile white shrimp (Litopenaeus setiferus) in tidal creek subsystems of the Duplin River, Sapelo Island, Georgia. Over a period of two years, 15,974 juvenile shrimp (40−80 mm TL) were marked internally with uniquely coded microwire tags and released in the shallow upper reaches of four salt marsh tidal creeks. Subsequent samples were taken every 3−6 days from channel segments arranged at 200-m intervals along transects extending from the upper to lower reach of each tidal creek. These collections included 201,384 juvenile shrimp, of which 184 were marked recaptures. Recaptured shrimp were at large an average of 3−4 weeks (range: 2−99 days) and were recovered a mean distance of <0.4 km from where they were initially marked. Mean residence times in the creek subsystems ranged from 15.2 to 25.5 days and were estimated from exponential decay functions describing the proportions of marked individuals recaptured with increasing days at large. Residence time was not significantly correlated with creek length (Pearson=−0.316, P=0.684 ), but there was suggestive evidence of positive associations with either intertidal (Pearson r=0.867, P=0.133) or subtidal (Pearson r=0.946, P=0.054) drainage area. Daily mean specific growth rates averaged 0.009 to 0.013 among creeks; mean absolute growth rates ranged from 0.56−0.84 mm/d, and were lower than those previously reported for juvenile penaeids in estuaries of the southeastern United States. Mean individual growth rates were not significantly different between years (t-test, P>0.30) but varied significantly during the season, tending to be greater in July than November. Growth rates were size-dependent, and temporal changes in size distributions rather than temporal variation in physical environmental factors may have accounted for seasonal differences in growth. Growth rates differed between creeks in 1999 (t-test, P<0.015), but not in 1998 (t-test, P>0.5). We suggest that spatial variation in landscape structure associated with access to intertidal resources may have accounted for this apparent interannual difference in growth response.
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Ninety-six bigeye tuna (88– 134 cm fork length) were caught and released with implanted archival (electronic data storage) tags near fish-aggregating devices (FADs) in the equatorial eastern Pacific Ocean (EPO) during April 2000. Twenty-nine fish were recaptured, and the data from twenty-seven tags were successfully downloaded and processed. Time at liberty ranged from 8 to 446 days, and data for 23 fish at liberty for 30 days or more are presented. The accuracy in geolocation estimates, derived from the light level data, is about 2 degrees in latitude and 0.5 degrees in longitude in this region. The movement paths derived from the filtered geolocation estimates indicated that none of the fish traveled west of 110°W during the period between release and recapture. The null hypothesis that the movement path is random was rejected in 17 of the 22 statistical tests of the observed movement paths. The estimated mean velocity was 117 km/d. The fish exhibited occasional deep-diving behavior, and some dives exceeded 1000 m where temperatures were less than 3°C. Evaluations of timed depth records, resulted in the discrimination of three distinct behaviors: 54.3% of all days were classified as unassociated (with a floating object) type-1 behavior, 27.7% as unassociated type-2 behavior, and 18.7% as behavior associated with a floating object. The mean residence time at floating objects was 3.1 d. Data sets separated into day and night were used to evaluate diel differences in behavior and habitat selection. When the fish were exhibiting unassociated type-1 behavior (diel vertical migrations), they were mostly at depths of less than 50 m (within the mixed layer) throughout the night, and during the day between 200 and 300 m and 13° and 14°C. They shifted their average depths in conjunction with dawn and dusk events, presumably tracking the deep-scattering layer as a foraging strategy. There were also observed changes in the average nighttime depth distributions of the fish in relation to moon phase.