Filtration and oxidation characteristics of a diesel oxidation catalyst and a catalyzed particulate filter : development of a 1-D 2-layer model

The emissions, filtration and oxidation characteristics of a diesel oxidation catalyst (DOC) and a catalyzed particulate filter (CPF) in a Johnson Matthey catalyzed continuously regenerating trap (CCRT ®) were studied by using computational models. Experimental data needed to calibrate the models were obtained by characterization experiments with raw exhaust sampling from a Cummins ISM 2002 engine with variable geometry turbocharging (VGT) and programmed exhaust gas recirculation (EGR). The experiments were performed at 20, 40, 60 and 75% of full load (1120 Nm) at rated speed (2100 rpm), with and without the DOC upstream of the CPF. This was done to study the effect of temperature and CPF-inlet NO2 concentrations on particulate matter oxidation in the CCRT ®. A previously developed computational model was used to determine the kinetic parameters describing the oxidation characteristics of HCs, CO and NO in the DOC and the pressure drop across it. The model was calibrated at five temperatures in the range of 280 – 465° C, and exhaust volumetric flow rates of 0.447 – 0.843 act-m3/sec. The downstream HCs, CO and NO concentrations were predicted by the DOC model to within ±3 ppm. The HCs and CO oxidation kinetics in the temperature range of 280 - 465°C and an exhaust volumetric flow rate of 0.447 - 0.843 act-m3/sec can be represented by one ’apparent’ activation energy and pre-exponential factor. The NO oxidation kinetics in the same temperature and exhaust flow rate range can be represented by ’apparent’ activation energies and pre-exponential factors in two regimes. The DOC pressure drop was always predicted within 0.5 kPa by the model. The MTU 1-D 2-layer CPF model was enhanced in several ways to better model the performance of the CCRT ®. A model to simulate the oxidation of particulate inside the filter wall was developed. A particulate cake layer filtration model which describes particle filtration in terms of more fundamental parameters was developed and coupled to the wall oxidation model. To better model the particulate oxidation kinetics, a model to take into account the NO2 produced in the washcoat of the CPF was developed. The overall 1-D 2-layer model can be used to predict the pressure drop of the exhaust gas across the filter, the evolution of particulate mass inside the filter, the particulate mass oxidized, the filtration efficiency and the particle number distribution downstream of the CPF. The model was used to better understand the internal performance of the CCRT®, by determining the components of the total pressure drop across the filter, by classifying the total particulate matter in layer I, layer II, the filter wall, and by the means of oxidation i.e. by O2, NO2 entering the filter and by NO2 being produced in the filter. The CPF model was calibrated at four temperatures in the range of 280 – 465 °C, and exhaust volumetric flow rates of 0.447 – 0.843 act-m3/sec, in CPF-only and CCRT ® (DOC+CPF) configurations. The clean filter wall permeability was determined to be 2.00E-13 m2, which is in agreement with values in the literature for cordierite filters. The particulate packing density in the filter wall had values between 2.92 kg/m3 - 3.95 kg/m3 for all the loads. The mean pore size of the catalyst loaded filter wall was found to be 11.0 µm. The particulate cake packing densities and permeabilities, ranged from 131 kg/m3 - 134 kg/m3, and 0.42E-14 m2 and 2.00E-14 m2 respectively, and are in agreement with the Peclet number correlations in the literature. Particulate cake layer porosities determined from the particulate cake layer filtration model ranged between 0.841 and 0.814 and decreased with load, which is about 0.1 lower than experimental and more complex discrete particle simulations in the literature. The thickness of layer I was kept constant at 20 µm. The model kinetics in the CPF-only and CCRT ® configurations, showed that no ’catalyst effect’ with O2 was present. The kinetic parameters for the NO2-assisted oxidation of particulate in the CPF were determined from the simulation of transient temperature programmed oxidation data in the literature. It was determined that the thermal and NO2 kinetic parameters do not change with temperature, exhaust flow rate or NO2 concentrations. However, different kinetic parameters are used for particulate oxidation in the wall and on the wall. Model results showed that oxidation of particulate in the pores of the filter wall can cause disproportionate decreases in the filter pressure drop with respect to particulate mass. The wall oxidation model along with the particulate cake filtration model were developed to model the sudden and rapid decreases in pressure drop across the CPF. The particulate cake and wall filtration models result in higher particulate filtration efficiencies than with just the wall filtration model, with overall filtration efficiencies of 98-99% being predicted by the model. The pre-exponential factors for oxidation by NO2 did not change with temperature or NO2 concentrations because of the NO2 wall production model. In both CPF-only and CCRT ® configurations, the model showed NO2 and layer I to be the dominant means and dominant physical location of particulate oxidation respectively. However, at temperatures of 280 °C, NO2 is not a significant oxidizer of particulate matter, which is in agreement with studies in the literature. The model showed that 8.6 and 81.6% of the CPF-inlet particulate matter was oxidized after 5 hours at 20 and 75% load in CCRT® configuration. In CPF-only configuration at the same loads, the model showed that after 5 hours, 4.4 and 64.8% of the inlet particulate matter was oxidized. The increase in NO2 concentrations across the DOC contributes significantly to the oxidation of particulate in the CPF and is supplemented by the oxidation of NO to NO2 by the catalyst in the CPF, which increases the particulate oxidation rates. From the model, it was determined that the catalyst in the CPF modeslty increases the particulate oxidation rates in the range of 4.5 – 8.3% in the CCRT® configuration. Hence, the catalyst loading in the CPF of the CCRT® could possibly be reduced without significantly decreasing particulate oxidation rates leading to catalyst cost savings and better engine performance due to lower exhaust backpressures.

Lava discharge rate estimates from thermal infrared satellite data at Pacaya Volcano, Guatemala

Time-averaged discharge rates (TADR) were calculated for five lava flows at Pacaya Volcano (Guatemala), using an adapted version of a previously developed satellite-based model. Imagery acquired during periods of effusive activity between the years 2000 and 2010 were obtained from two sensors of differing temporal and spatial resolutions; the Moderate Resolution Imaging Spectroradiometer (MODIS), and the Geostationary Operational Environmental Satellites (GOES) Imager. A total of 2873 MODIS and 2642 GOES images were searched manually for volcanic “hot spots”. It was found that MODIS imagery, with superior spatial resolution, produced better results than GOES imagery, so only MODIS data were used for quantitative analyses. Spectral radiances were transformed into TADR via two methods; first, by best-fitting some of the parameters (i.e. density, vesicularity, crystal content, temperature change) of the TADR estimation model to match flow volumes previously estimated from ground surveys and aerial photographs, and second by measuring those parameters from lava samples to make independent estimates. A relatively stable relationship was defined using the second method, which suggests the possibility of estimating lava discharge rates in near-real-time during future volcanic crises at Pacaya.

Estimation and calibration of the water isotope differential diffusion length in ice core records

Palaeoclimatic information can be retrieved from the diffusion of the stable water isotope signal during firnification of snow. The diffusion length, a measure for the amount of diffusion a layer has experienced, depends on the firn temperature and the accumulation rate. We show that the estimation of the diffusion length using power spectral densities (PSDs) of the record of a single isotope species can be biased by uncertainties in spectral properties of the isotope signal prior to diffusion. By using a second water isotope and calculating the difference in diffusion lengths between the two isotopes, this problem is circumvented. We study the PSD method applied to two isotopes in detail and additionally present a new forward diffusion method for retrieving the differential diffusion length based on the Pearson correlation between the two isotope signals. The two methods are discussed and extensively tested on synthetic data which are generated in a Monte Carlo manner. We show that calibration of the PSD method with this synthetic data is necessary to be able to objectively determine the differential diffusion length. The correlation-based method proves to be a good alternative for the PSD method as it yields precision equal to or somewhat higher than the PSD method. The use of synthetic data also allows us to estimate the accuracy and precision of the two methods and to choose the best sampling strategy to obtain past temperatures with the required precision. In addition to application to synthetic data the two methods are tested on stable-isotope records from the EPICA (European Project for Ice Coring in Antarctica) ice core drilled in Dronning Maud Land, Antarctica, showing that reliable firn temperatures can be reconstructed with a typical uncertainty of 1.5 and 2 °C for the Holocene period and 2 and 2.5 °C for the last glacial period for the correlation and PSD method, respectively.

STUDIES ON THE PATTERNS OF NUCLEOTIDE AND AMINO ACID SUBSTITUTION (ELECTROPHORESIS, MUTATION RATE, SELECTION, BASE, COMPOSITION)

Theoretical and empirical studies were conducted on the pattern of nucleotide and amino acid substitution in evolution, taking into account the effects of mutation at the nucleotide level and purifying selection at the amino acid level. A theoretical model for predicting the evolutionary change in electrophoretic mobility of a protein was also developed by using information on the pattern of amino acid substitution. The specific problems studied and the main results obtained are as follows: (1) Estimation of the pattern of nucleotide substitution in DNA nuclear genomes. The pattern of point mutations and nucleotide substitutions among the four different nucleotides are inferred from the evolutionary changes of pseudogenes and functional genes, respectively. Both patterns are non-random, the rate of change varying considerably with nucleotide pair, and that in both cases transitions occur somewhat more frequently than transversions. In protein evolution, substitution occurs more often between amino acids with similar physico-chemical properties than between dissimilar amino acids. (2) Estimation of the pattern of nucleotide substitution in RNA genomes. The majority of mutations in retroviruses accumulate at the reverse transcription stage. Selection at the amino acid level is very weak, and almost non-existent between synonymous codons. The pattern of mutation is very different from that in DNA genomes. Nevertheless, the pattern of purifying selection at the amino acid level is similar to that in DNA genomes, although selection intensity is much weaker. (3) Evaluation of the determinants of molecular evolutionary rates in protein-coding genes. Based on rates of nucleotide substitution for mammalian genes, the rate of amino acid substitution of a protein is determined by its amino acid composition. The content of glycine is shown to correlate strongly and negatively with the rate of substitution. Empirical formulae, called indices of mutability, are developed in order to predict the rate of molecular evolution of a protein from data on its amino acid sequence. (4) Studies on the evolutionary patterns of electrophoretic mobility of proteins. A theoretical model was constructed that predicts the electric charge of a protein at any given pH and its isoelectric point from data on its primary and quaternary structures. Using this model, the evolutionary change in electrophoretic mobilities of different proteins and the expected amount of electrophoretically hidden genetic variation were studied. In the absence of selection for the pI value, proteins will on the average evolve toward a mildly basic pI. (Abstract shortened with permission of author.) ^

Using small area estimation and geographic information systems technology to target health services for the uninsured

The three articles that comprise this dissertation describe how small area estimation and geographic information systems (GIS) technologies can be integrated to provide useful information about the number of uninsured and where they are located. Comprehensive data about the numbers and characteristics of the uninsured are typically only available from surveys. Utilization and administrative data are poor proxies from which to develop this information. Those who cannot access services are unlikely to be fully captured, either by health care provider utilization data or by state and local administrative data. In the absence of direct measures, a well-developed estimation of the local uninsured count or rate can prove valuable when assessing the unmet health service needs of this population. However, the fact that these are “estimates” increases the chances that results will be rejected or, at best, treated with suspicion. The visual impact and spatial analysis capabilities afforded by geographic information systems (GIS) technology can strengthen the likelihood of acceptance of area estimates by those most likely to benefit from the information, including health planners and policy makers. ^ The first article describes how uninsured estimates are currently being performed in the Houston metropolitan region. It details the synthetic model used to calculate numbers and percentages of uninsured, and how the resulting estimates are integrated into a GIS. The second article compares the estimation method of the first article with one currently used by the Texas State Data Center to estimate numbers of uninsured for all Texas counties. Estimates are developed for census tracts in Harris County, using both models with the same data sets. The results are statistically compared. The third article describes a new, revised synthetic method that is being tested to provide uninsured estimates at sub-county levels for eight counties in the Houston metropolitan area. It is being designed to replicate the same categorical results provided by a current U.S. Census Bureau estimation method. The estimates calculated by this revised model are compared to the most recent U.S. Census Bureau estimates, using the same areas and population categories. ^

Current and potential water erosion estimation with RUSLE3D in Castellon province (Spain)

The purpose of this study was the estimation of current and potential water erosion rates in Castellon Province (Spain) using RUSLE3D (Revised Universal Soil Loss Equation-3D) model with Geographical Information System (GIS) support. RUSLE3D uses a new methodology for topographic factor estimation (LS factor) based on the impact of flow convergence allowing better assessment of sediment distribution detached by water erosion. In RUSLE3D equation, the effect that vegetation cover has on soil erosion rate is reflected by the C factor. Potential erosion indicates soil erosion rate without considering C factor in RUSLE3D equation. The results showed that 57% of estimated current erosion does not exceed 10 t/ha.year (low erosion). In the case of potential erosion rates, 5% of the area of Castellon Province does not exceed 10 t/ha.year but 55% exceed 200 t/ha.year. Based on these results, the current vegetation cover of Castellon Province is adequate but needs to be conserved to avoid an increase in the current soil erosion rates as shown by potential erosion rates.

Ingestion rate and egg production of copepods collected in the upper 20m in the eastern Mediterranean Sea in April 2008 during SES_GR2

The ingestion on ciliates and phytoplankton dataset is based on samples taken during October 2008 in Northern Aegean Sea, the area influenced by the Black Sea water outflow. A Lagrangian experiment was established and copepod ingestion was estimated from experiments performed at stations according to the different positions of drifters during the cruise. Copepods for the experiments were obtained with slow non-quantitative tows from the upper 20 m layer of the water column using 200 µm mesh size nets fitted with a large non-filtering cod end. For the grazing experiments we used the following copepod species: Clausocalanus furcatus, and Temoraa stylifera according to the relevant reference (Bamstedt et al. 2000). Copepod clearance rates on ciliates were calculated according to Frost equations (Frost 1972). Ingestion rates were calculated by multiplying clearance rates by the initial standing stocks (Bamstedt et al. 2000). The egg production dataset is based on samples taken during October 2008 in Northern Aegean Sea, the area influenced by the Black Sea water outflow. A Lagrangian experiment was established and copepod egg production was estimated from experiments performed at stations according to the different positions of drifters during the cruise. Egg production rates of the dominant calanoid copepods were determined by incubation of fertilised females (eggs female/day) collected in the 0-20m layer. Copepod egg production was measured for the copepods Clausocalanus furcatus, Temora stylifera. On board experiments for the estimation of copepod egg production were taken place. For the estimation of copepod production (mgC/m**2/day), lengths (copepods and eggs) were converted to body carbon (Hopcroft et al., 1998) and production was estimated from biomass and weight-specific egg production rates, by assuming that those rates are representative for juvenile specific growth rates (Berggreen et al., 1988).

Cretaceous stable isotopic record and sea surface temperture estimation for ODP Site 207-1259

The Turonian (93.5 to 89.3 million years ago) was one of the warmest periods of the Phanerozoic eon, with tropical sea surface temperatures over 35°C. High-amplitude sea-level changes and positive d18O excursions in marine limestones suggest that glaciation events may have punctuated this episode of extreme warmth. New d18O data from the tropical Atlantic show synchronous shifts ~91.2 million years ago for both the surface and deep ocean that are consistent with an approximately 200,000-year period of glaciation, with ice sheets of about half the size of the modern Antarctic ice cap. Even the prevailing supergreenhouse climate was not a barrier to the formation of large ice sheets, calling into question the common assumption that the poles were always ice-free during past periods of intense global warming.

Ingestion rate and egg production of copepods collected in the Turkish Strait during Bilim 2 cruise in April 2008

The copepod Ingestion on ciliates, phytoplankton and the copepod production dataset is based on samples taken during April 2008 in Dardanelles Straits, Marmara Sea and Bosporus Straits at the third priority stations. These experiments were set up according to DoW of Sesame project. Copepods for the experiments were obtained with slow non-quantitative tows from the upper 50 m layer of the water column using 200 µm mesh size nets fitted with a large non-filtering cod end. For the grazing experiments we used the following copepod species: Centropages typicus and Acartia clausi according to the relevant reference (Bamstedt et al. 2000). Copepod clearance rates on ciliates were calculated according to Frost equations (Frost 1972). Ingestion rates were calculated by multiplying clearance rates by the initial standing stocks (Bamstedt et al. 2000). Egg production rates of the dominant calanoid copepods were determined by incubation of fertilised females (eggs/female/day) collected in the 0-20m layer. Copepod egg production was measured for the copepods Centropages typicus and Acartia clausi. On board experiments for the estimation of copepod egg production were taken place. For the estimation of copepod production (mg/m**2/day), lengths (copepods and eggs) were converted to body carbon (Hopcroft et al., 1998) and production was estimated from biomass and weight-specific egg production rates, by assuming that those rates are representative for juvenile specific growth rates (Berggreen et al., 1988).

Stable isotope ratios of foraminifera and sea surface temperature estimation of sediment core W2804A-14

Carbon isotopically based estimates of CO2 levels have been generated from a record of the photosynthetic fractionation of 13C (epsilon p) in a central equatorial Pacific sediment core that spans the last ~255 ka. Contents of 13C in phytoplanktonic biomass were determined by analysis of C37 alkadienones. These compounds are exclusive products of Prymnesiophyte algae which at present grow most abundantly at depths of 70-90 m in the central equatorial Pacific. A record of the isotopic compostion of dissolved CO2 was constructed from isotopic analyses of the planktonic foraminifera Neogloboquadrina dutertrei, which calcifies at 70-90 m in the same region. Values of epsilon p, derived by comparison of the organic and inorganic delta values, were transformed to yield concentrations of dissolved CO2 (c e) based on a new, site-specific calibration of the relationship between epsilon p and c e. The calibration was based on reassessment of existing epsilon p versus c e data, which support a physiologically based model in which epsilon p is inversely related to c e. Values of PCO2, the partial pressure of CO2 that would be in equilibrium with the estimated concentrations of dissolved CO2, were calculated using Henry's law and the temperature determined from the alkenone-unsaturation index UK 37. Uncertainties in these values arise mainly from uncertainties about the appropriateness (particularly over time) of the site-specific relationship between epsilon p and 1/c e. These are discussed in detail and it is concluded that the observed record of epsilon p most probably reflects significant variations in Delta pCO2, the ocean-atmosphere disequilibrium, which appears to have ranged from ~110 µatm during glacial intervals (ocean > atmosphere) to ~60 µatm during interglacials. Fluxes of CO2 to the atmosphere would thus have been significantly larger during glacial intervals. If this were characteristic of large areas of the equatorial Pacific, then greater glacial sinks for the equatorially evaded CO2 must have existed elsewhere. Statistical analysis of air-sea pCO2 differences and other parameters revealed significant (p < 0.01) inverse correlations of Delta pCO2 with sea surface temperature and with the mass accumulation rate of opal. The former suggests response to the strength of upwelling, the latter may indicate either drawdown of CO2 by siliceous phytoplankton or variation of [CO2]/[Si(OH)4] ratios in upwelling waters.

Sea surface temperature estimation for the last 70 ka from IODP Site 306-U1313

During the six Heinrich Events of the last 70 ka episodic calving from the circum-Atlantic ice sheets released large numbers of icebergs into the North Atlantic. These icebergs and associated melt-water flux are hypothesized to have led to a shutdown of Atlantic Meridional Overturning Circulation (AMOC) and severe cooling in large parts of the Northern Hemisphere. However, due to the limited availability of high-resolution records the magnitude sea surface temperature (SST) changes related to the impact of Heinrich Events on the mid-latitude North Atlantic is poorly constrained. Here we present a record of UK37'-based SSTs derived from sediments of Integrated Ocean Drilling Project (IODP) Site U1313, located at the southern end of the ice-rafted debris (IRD)-belt in the mid-latitude North Atlantic (41°N). We demonstrate that all six Heinrich Events are associated with a rapid warming of surface waters by 2 to 4°C in a few thousand years. The presence of IRD leaves no doubt about the simultaneous timing and correlation between rapid surface water warming and Heinrich Events. We argue that this warming in the mid-latitude North Atlantic is related to a northward expansion of the subtropical gyre during Heinrich Events. As a wide-range of studies demonstrated that in the central IRD-belt Heinrich Events are associated with low SSTs, these results thus identify an anti-phased (seesaw) pattern in SSTs during Heinrich Events between the mid-latitude (warm) and northern North Atlantic (cold). This highlights the complex response of surface water characteristics in the North Atlantic to Heinrich Events that is poorly reproduced by fresh water hosing experiments and challenges the widely accepted view that within the IRD-belt of the North Atlantic Heinrich Events coincide with periods of low SSTs.

Literature review of elasmobranch bycatch and retention rate

To address growing concern over the effects of fisheries non-target catch on elasmobranchs worldwide, the accurate reporting of elasmobranch catch is essential. This requires data on a combination of measures, including reported landings, retained and discarded non-target catch, and post-discard survival. Identification of the factors influencing discard vs. retention is needed to improve catch estimates and to determine wasteful fishing practices. To do this we compared retention rates of elasmobranch non-target catch in a broad subset of fisheries throughout the world by taxon, fishing country, and gear. A regression tree and random forest analysis indicated that taxon was the most important determinant of retention in this dataset, but all three factors together explained 59% of the variance. Estimates of total elasmobranch removals were calculated by dividing the FAO global elasmobranch landings by average retention rates and suggest that total elasmobranch removals may exceed FAO reported landings by as much as 400%. This analysis is the first effort to directly characterize global drivers of discards for elasmobranch non-target catch. Our results highlight the importance of accurate quantification of retention and discard rates to improve assessments of the potential impacts of fisheries on these species.

Fecal pellet ingestion rate and feeding behavior of Oithona similis, Calanus helgolandicus and Pseudocalanus elongatus from the North Sea

Studies of fecal pellet flux show that a large percentage of pellets produced in the upper ocean is degraded within the surface waters. It is therefore important to investigate these degradation mechanisms to understand the role of fecal pellets in the oceanic carbon cycle. Degradation of pellets is mainly thought to be caused by coprophagy (ingestion of fecal pellets) by copepods, and especially by the ubiquitous copepods Oithona spp. We examined fecal pellet ingestion rate and feeding behavior of O. similis and 2 other dominant copepod species from the North Sea (Calanus helgolandicus and Pseudocalanus elongatus). All investigations were done with fecal pellets as the sole food source and with fecal pellets offered together with an alternative suitable food source. The ingestion of fecal pellets by all 3 copepod species was highest when offered together with an alternative food source. No feeding behavior was determined for O. similis due to the lack of pellet capture in those experiments. Fecal pellets offered together with an alternative food source increased the filtration activity by C. helgolandicus and P. elongatus and thereby the number of pellets caught in their feeding current. However, most pellets were rejected immediately after capture and were often fragmented during rejection. Actual ingestion of captured pellets was rare (<37% for C. helgolandicus and <24% for P. elongatus), and only small pellet fragments were ingested unintentionally along with alternative food. We therefore suggest coprorhexy (fragmentation of pellets) to be the main effect of copepods on the vertical flux of fecal pellets. Coprorhexy turns the pellets into smaller, slower-sinking particles that can then be degraded by other organisms such as bacteria and protozooplankton.

Sea surface temperature estimation for MIS 16 of IODP Site 306-U1313

Hudson Strait (HS) Heinrich Events, ice-rafting events in the North Atlantic originating from the Laurentide ice sheet (LIS), are among the most dramatic examples of millennial-scale climate variability and have a large influence on global climate. However, it is debated as to whether the occurrence of HS Heinrich Events in the (eastern) North Atlantic in the geological record depends on greater ice discharge, or simply from the longer survival of icebergs in cold waters. Using sediments from Integrated Ocean Drilling Program (IODP) Site U1313 in the North Atlantic spanning the period between 960 and 320 ka, we show that sea surface temperatures (SSTs) did not control the first occurrence of HS Heinrich(-like) Events in the sedimentary record. Using mineralogy and organic geochemistry to determine the characteristics of ice-rafting debris (IRD), we detect the first HS Heinrich(-like) Event in our record around 643 ka (Marine Isotope Stage (MIS) 16), which is similar as previously reported for Site U1308. However, the accompanying high-resolution alkenone-based SST record demonstrates that the first HS Heinrich(-like) Event did not coincide with low SSTs. Thus, the HS Heinrich(-like) Events do indicate enhanced ice discharge from the LIS at the end of the Mid-Pleistocene Transition, not simply the survivability of icebergs due to cold conditions in the North Atlantic.