An extended regression approach to estimating loads and their uncertainties in Great Barrier Reef catchments

There are numerous load estimation methods available, some of which are captured in various online tools. However, most estimators are subject to large biases statistically, and their associated uncertainties are often not reported. This makes interpretation difficult and the estimation of trends or determination of optimal sampling regimes impossible to assess. In this paper, we first propose two indices for measuring the extent of sampling bias, and then provide steps for obtaining reliable load estimates by minimizing the biases and making use of possible predictive variables. The load estimation procedure can be summarized by the following four steps: - (i) output the flow rates at regular time intervals (e.g. 10 minutes) using a time series model that captures all the peak flows; - (ii) output the predicted flow rates as in (i) at the concentration sampling times, if the corresponding flow rates are not collected; - (iii) establish a predictive model for the concentration data, which incorporates all possible predictor variables and output the predicted concentrations at the regular time intervals as in (i), and; - (iv) obtain the sum of all the products of the predicted flow and the predicted concentration over the regular time intervals to represent an estimate of the load. The key step to this approach is in the development of an appropriate predictive model for concentration. This is achieved using a generalized regression (rating-curve) approach with additional predictors that capture unique features in the flow data, namely the concept of the first flush, the location of the event on the hydrograph (e.g. rise or fall) and cumulative discounted flow. The latter may be thought of as a measure of constituent exhaustion occurring during flood events. The model also has the capacity to accommodate autocorrelation in model errors which are the result of intensive sampling during floods. Incorporating this additional information can significantly improve the predictability of concentration, and ultimately the precision with which the pollutant load is estimated. We also provide a measure of the standard error of the load estimate which incorporates model, spatial and/or temporal errors. This method also has the capacity to incorporate measurement error incurred through the sampling of flow. We illustrate this approach using the concentrations of total suspended sediment (TSS) and nitrogen oxide (NOx) and gauged flow data from the Burdekin River, a catchment delivering to the Great Barrier Reef. The sampling biases for NOx concentrations range from 2 to 10 times indicating severe biases. As we expect, the traditional average and extrapolation methods produce much higher estimates than those when bias in sampling is taken into account.

Copper Diffusion Barrier Deposition on Integrated Circuit Devices by Atomic Layer Deposition Technique

Transfer from aluminum to copper metallization and decreasing feature size of integrated circuit devices generated a need for new diffusion barrier process. Copper metallization comprised entirely new process flow with new materials such as low-k insulators and etch stoppers, which made the diffusion barrier integration demanding. Atomic Layer Deposition technique was seen as one of the most promising techniques to deposit copper diffusion barrier for future devices. Atomic Layer Deposition technique was utilized to deposit titanium nitride, tungsten nitride, and tungsten nitride carbide diffusion barriers. Titanium nitride was deposited with a conventional process, and also with new in situ reduction process where titanium metal was used as a reducing agent. Tungsten nitride was deposited with a well-known process from tungsten hexafluoride and ammonia, but tungsten nitride carbide as a new material required a new process chemistry. In addition to material properties, the process integration for the copper metallization was studied making compatibility experiments on different surface materials. Based on these studies, titanium nitride and tungsten nitride processes were found to be incompatible with copper metal. However, tungsten nitride carbide film was compatible with copper and exhibited the most promising properties to be integrated for the copper metallization scheme. The process scale-up on 300 mm wafer comprised extensive film uniformity studies, which improved understanding of non-uniformity sources of the ALD growth and the process-specific requirements for the ALD reactor design. Based on these studies, it was discovered that the TiN process from titanium tetrachloride and ammonia required the reactor design of perpendicular flow for successful scale-up. The copper metallization scheme also includes process steps of the copper oxide reduction prior to the barrier deposition and the copper seed deposition prior to the copper metal deposition. Easy and simple copper oxide reduction process was developed, where the substrate was exposed gaseous reducing agent under vacuum and at elevated temperature. Because the reduction was observed efficient enough to reduce thick copper oxide film, the process was considered also as an alternative method to make the copper seed film via copper oxide reduction.

Quantum theoretical study of molecular mechanisms of mutation and cancer - A review

Several endogenous and exogenous chemical species, particularly the so-called reactive oxygen species (ROS) and reactive nitrogen oxide species (RNOS), attack deoxyribonucleic acid (DNA) in biological systems producing DNA lesions which hamper normal cell functioning and cause various diseases including mutation and cancer. The guanine (G) base of DNA among all the bases is most susceptible and certain modified guanines get involved in mispairing with other bases during DNA replication. The biological system repairs the abnormal base pairs, but those that are still left cause mutation and cancer. Anti-oxidants present in biological systems can scavenge the ROS and RNOS. Thus three types of molecular events occur in biological media: (i) DNA damage, (ii) DNA repair, and (iii) prevention of DNA damage by scavenging ROS and RNOS. Quantum mechanical methods may be used to unravel molecular mechanisms of such phenomena. Some recent quantum theoretical results obtained on these problems are reviewed here.

Estudio de la reducción de SO2 con CH4 en presencia de O2 a altas temperaturas, sobre catalizador de Cr2O3 soportado en alúmina

Resumen: Se propone utilizar un óxido como el Cr2O3 como catalizador ya que se ha determinado anteriormente, en la primera etapa de esta investigación, (“Estudio comparativo de la retención de SO2 sobre óxidos de metales de transición soportados en alúmina”), que la retención de SO2 sobre su superficie es un proceso de quimisorción con formación de especies sulfito superficiales sobre sitios básicos y un proceso de óxido reducción del ión metálico. Apoya este mecanismo el hecho de que la cantidad de SO2 adsorbido es función de la temperatura. La mayor eficiencia del Cr2O3 puede explicarse en base a sus propiedades superficiales, lo cual ha sido utilizado en la segunda etapa de reacción de reducción, ya que se ha completado la etapa inicial de quimisorción. En la segunda etapa de esta investigación (“Estudio de la reacción de reducción de SO2 con CH4 a altas temperaturas sobre catalizador de Cr2O3 soportado en alúmina”), se apuntó al estudio de un nuevo tipo de sinergia entre propiedades ácido-base y propiedades redox en una misma superficie. Esta tercera etapa apuntó a determinar la influencia que tiene el O2 en este proceso, ya que el O2 se encuentra presente en las chimeneas industriales en las condiciones de reacción entre el SO2 y el CH4, y produce modificaciones en los parámetros de reacción. Se experimentó con diferentes masas de catalizador y flujos de los distintos gases, y se estudió la influencia de la presencia de oxígeno en la reacción y particularmente con diferentes flujos del mismo, y la posibilidad de regeneración del catalizador.

Estudio de la factibilidad de aplicación, a escala planta piloto, del catalizador Cr2O3, soportado en alúmina, en la reducción de emisión de SO2 a la atmósfera proveniente de fuentes fijas

Resumen: Se propone utilizar un óxido como el Cr2O3 como catalizador ya que se ha determinado anteriormente, en la primera etapa de esta investigación, (“Estudio comparativo de la retención de SO2 sobre óxidos de metales de transición soportados en alúmina”), que la retención de SO2 sobre su superficie es un proceso de quimisorción con formación de especies sulfito superficiales sobre sitios básicos y un proceso de óxido reducción del ión metálico. Apoya este mecanismo el hecho de que la cantidad de SO2 adsorbido es función de la temperatura. La mayor eficiencia del Cr2O3 puede explicarse en base a sus propiedades superficiales, lo cual ha sido utilizado en la segunda etapa de reacción de reducción, ya que se ha completado la etapa inicial de quimisorción. En la segunda etapa de esta investigación (“Estudio de la reacción de reducción de SO2 con CH4 a altas temperaturas sobre catalizador de Cr2O3 soportado en alúmina”), se apuntó al estudio de un nuevo tipo de sinergia entre propiedades ácido-base y propiedades redox en una misma superficie. La tercera etapa apuntó a determinar la influencia que tiene el O2 en este proceso, ya que el O2 se encuentra presente en las chimeneas industriales en las condiciones de reacción entre el SO2 y el CH4, y produce modificaciones en los parámetros de reacción. Se experimentó con diferentes masas de catalizador y flujos de los distintos gases, y se estudió la influencia de la presencia de oxígeno en la reacción y particularmente con diferentes flujos del mismo, y la posibilidad de regeneración del catalizador.En esta cuarta y última etapa se están estudiando los cambios que se producen en la reacción al pasar de escala laboratorio a planta piloto utilizando una columna de mayor diámetro construída en metal. A través de los datos experimentales se está estudiando, en conjunto con el INIFTA, la presencia de especies sulfito y sulfato sobre la superficie del soporte. Adicionalmente, por medio del programa VASP (Vienna Ab-initio Simulation Package), se analiza la interacción entre los reactivos gaseosos y el soporte.

Income, inequality, and criteria air pollutants in the CAMA counties

Socioeconomic factors have long been incorporated into environmental research to examine the effects of human dimensions on coastal natural resources. Boyce (1994) proposed that inequality is a cause of environmental degradation and the Environmental Kuznets Curve is a proposed relationship that income or GDP per capita is related with initial increases in pollution followed by subsequent decreases (Torras and Boyce, 1998). To further examine this relationship within the CAMA counties, the emission of sulfur dioxide and nitrogen oxides, as measured by the EPA in terms of tons emitted, the Gini Coefficient, and income per capita were examined for the year of 1999. A quadratic regression was utilized and the results did not indicate that inequality, as measured by the Gini Coefficient, was significantly related to the level of criteria air pollutants within each county. Additionally, the results did not indicate the existence of the Environmental Kuznets Curve. Further analysis of spatial autocorrelation using ArcMap 9.2, found a high level of spatial autocorrelation among pollution emissions indicating that relation to other counties may be more important to the level of sulfur dioxide and nitrogen oxide emissions than income per capita and inequality. Lastly, the paper concludes that further Environmental Kuznets Curve and income inequality analyses in regards to air pollutant levels incorporate spatial patterns as well as other explanatory variables. (PDF contains 4 pages)

An economic air pollution control model-application : photochemical smog in Los Angeles County in 1975

An economic air pollution control model, which determines the least cost of reaching various air quality levels, is formulated. The model takes the form of a general, nonlinear, mathematical programming problem. Primary contaminant emission levels are the independent variables. The objective function is the cost of attaining various emission levels and is to be minimized subject to constraints that given air quality levels be attained.

The model is applied to a simplified statement of the photochemical smog problem in Los Angeles County in 1975 with emissions specified by a two-dimensional vector, total reactive hydrocarbon, (RHC), and nitrogen oxide, (NO_x), emissions. Air quality, also two-dimensional, is measured by the expected number of days per year that nitrogen dioxide, (NO₂), and mid-day ozone, (O₃), exceed standards in Central Los Angeles.

The minimum cost of reaching various emission levels is found by a linear programming model. The base or "uncontrolled" emission levels are those that will exist in 1975 with the present new car control program and with the degree of stationary source control existing in 1971. Controls, basically "add-on devices", are considered here for used cars, aircraft, and existing stationary sources. It is found that with these added controls, Los Angeles County emission levels [(1300 tons/day RHC, 1000 tons /day NO_x) in 1969] and [(670 tons/day RHC, 790 tons/day NO_x) at the base 1975 level], can be reduced to 260 tons/day RHC (minimum RHC program) and 460 tons/day NO_x (minimum NO_x program).

"Phenomenological" or statistical air quality models provide the relationship between air quality and emissions. These models estimate the relationship by using atmospheric monitoring data taken at one (yearly) emission level and by using certain simple physical assumptions, (e. g., that emissions are reduced proportionately at all points in space and time). For NO₂, (concentrations assumed proportional to NO_x emissions), it is found that standard violations in Central Los Angeles, (55 in 1969), can be reduced to 25, 5, and 0 days per year by controlling emissions to 800, 550, and 300 tons /day, respectively. A probabilistic model reveals that RHC control is much more effective than NO_x control in reducing Central Los Angeles ozone. The 150 days per year ozone violations in 1969 can be reduced to 75, 30, 10, and 0 days per year by abating RHC emissions to 700, 450, 300, and 150 tons/day, respectively, (at the 1969 NO_x emission level).

The control cost-emission level and air quality-emission level relationships are combined in a graphical solution of the complete model to find the cost of various air quality levels. Best possible air quality levels with the controls considered here are 8 O₃ and 10 NO₂ violations per year (minimum ozone program) or 25 O₃ and 3 NO₂ violations per year (minimum NO₂ program) with an annualized cost of $230,000,000 (above the estimated $150,000,000 per year for the new car control program for Los Angeles County motor vehicles in 1975).

Manganese: Minerals, Microbes, and the Evolution of Oxygenic Photosynthesis

Oxygenic photosynthesis fundamentally transformed our planet by releasing molecular oxygen and altering major biogeochemical cycles, and this exceptional metabolism relies on a redox-active cubane cluster of four manganese atoms. Not only is manganese essential for producing oxygen, but manganese is also only oxidized by oxygen and oxygen-derived species. Thus the history of manganese oxidation provides a valuable perspective on our planet’s environmental past, the ancient availability of oxygen, and the evolution of oxygenic photosynthesis. Broadly, the general trends of the geologic record of manganese deposition is a chronicle of ancient manganese oxidation: manganese is introduced into the fluid Earth as Mn(II) and it will remain only a trace component in sedimentary rocks until it is oxidized, forming Mn(III,IV) insoluble precipitates that are concentrated in the rock record. Because these manganese oxides are highly favorable electron acceptors, they often undergo reduction in sediments through anaerobic respiration and abiotic reaction pathways.

The following dissertation presents five chapters investigating manganese cycling both by examining ancient examples of manganese enrichments in the geologic record and exploring the mineralogical products of various pathways of manganese oxide reduction that may occur in sediments. The first chapter explores the mineralogical record of manganese and reports abundant manganese reduction recorded in six representative manganese-enriched sedimentary sequences. This is followed by a second chapter that further analyzes the earliest significant manganese deposit 2.4 billon years ago, and determines that it predated the origin of oxygenic photosynthesis and thus is supporting evidence for manganese-oxidizing photosynthesis as an evolutionary precursor prior to oxygenic photosynthesis. The lack of oxygen during this early manganese deposition was partially established using oxygen-sensitive detrital grains, and so a third chapter delves into what these grains mean for oxygen constraints using a mathematical model. The fourth chapter returns to processes affecting manganese post-deposition, and explores the relationships between manganese mineral products and (bio)geochemical reduction processes to understand how various manganese minerals can reveal ancient environmental conditions and biological metabolisms. Finally, a fifth chapter considers whether manganese can be mobilized and enriched in sedimentary rocks and determines that manganese was concentrated secondarily in a 2.5 billion-year-old example from South Africa. Overall, this thesis demonstrates how microbial processes, namely photosynthesis and metal oxide-reducing metabolisms, are linked to and recorded in the rich complexity of the manganese mineralogical record.

Heterometallic Complexes as Models of Enzymatic Active Sites

This dissertation describes studies on two multinucleating ligand architectures: the first scaffold was designed to support tricopper complexes, while the second platform was developed to support tri- and tetrametallic clusters.

In Chapter 2, the synthesis of yttrium (and lanthanide) complexes supported by a tripodal ligand framework designed to bind three copper centers in close proximity is described. Tricopper complexes were shown to react with dioxygen in a 1:1 [Cu₃]/O₂ stoichiometry to form intermediates in which the O–O bond was fully cleaved, as characterized via UV-Vis spectroscopy and determination of the reaction stoichiometry. Pre-arrangement of the three Cu centers was pivotal to cooperative O₂ activation, as mono-copper complexes reacted differently with dioxgyen. The reactivity of the observed intermediates was studied with various substrates (reductants, O-atom acceptors, H-atom donors, Brønsted acids) to determine their properties. In Chapter 3, the reactivity of the same yttrium-tricopper complex with nitric oxide was explored. Reductive coupling to form a trans-hyponitrite complex (characterized by X-ray crystallography) was observed via cooperative reactivity by an yttrium and a copper center on two distinct tetrametallic units. The hyponitrite complex was observed to release nitrous oxide upon treatment with a Brønsted acid, supporting its viability as an intermediate in nitric oxide reduction to nitrous oxide.

In Chapter 4, a different multinucleating ligand scaffold was employed to synthesize heterometallic triiron clusters containing one oxide and one hydroxide bridges. The effects of the redox-inactive, Lewis acidic heterometals on redox potential was studied by cyclic voltammetry, unveiling a linear correlation between redox potential and heterometal Lewis acidity. Further studies on these complexes showed that the Lewis acidity of the redox-inactive metals also affected the oxygen-atom transfer reactivity of these clusters. Comparisons of this reactivity with manganese systems, collaborative efforts to reassign the structures of related manganese oxo-hydroxo clusters, and synthetic attempts to access related dioxo clusters are also described.

In Appendix A, ongoing efforts to synthesize new clusters supported by the same multinucleating ligand platform are described. Studies of novel approaches towards ligand exchange in tetrametallic clusters and incorporation of new supporting and bridging ligand motifs in trinuclear complexes are presented.

Analysis of high pressure premixed flames using Equivalent Reactor Networks for predicting NOx emissions

This paper describes a computational study of lean premixed high pressure methane-air flames, using Computational Fluid Dynamics (CFD) together with a reactor network approach. A detailed chemical reaction mechanism is employed to predict pollutant concentrations, placing emphasis on nitrogen oxide emissions. The reacting flow field is divided into separate zones in which homogeneity of the physical and chemical conditions prevails. The defined zones are interconnected forming an Equivalent Reactor Network (ERN). Three flames are examined for which experimental data is available. Flame A is characterised by an equivalence ratio of 0.43 while Flames B and C are richer with equivalence ratios of 0.5 and 0.56 respectively. Computations are performed for a range of operating conditions, quantifying the effect in the emitted NOx levels. Model predictions are compared against the available experimental data. Sensitivity analysis is performed to investigate the effect of the network size, in order to define the optimum number of reactors for accurate predictions of the species mass fractions. © 2012 Elsevier Ltd. All rights reserved.

Characterization and catalytic behavior of La2-x(Sr,Th)(x)CuO4+/-lambda in reaction NO+CO

Two mixed oxide systems La2-xSrxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 1.0) and La2+xThxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 0.4) with K2NiF4 structure were prepared by varying re values; Their crystal structures were studied by means of XRD and IR spectra. The average valence of Cu ion at B site, nonstoichiometric oxygen (A) and the chemical composition in the bulk and on the surface of the catalysts were measured by means of chemical analysis and XPS. The catalytic behavior in reaction CO + NO was investigated under the regular change of average valence of Cu ion at B site and nonstoichiometric oxygen (lambda). Meanwhile, the adsorption and activation of the small molecules NO and the mixture of NO + CO over the mixed oxide catalysts were studied by means of MS-TPD. The catalytic mechanism of reaction NO + CO over these oxide catalysts were proposed; and it has been found that, at lower temperatures the activation of NO is the rate determining step and the catalytic activity is related to the lower valent metallic ion and its concentration, while at higher temperatures the adsorption of NO is the rate determining step and the catalytic activity is related to the oxygen vacancy and its concentration.

FLOW-INJECTION ANALYSIS OF MYOGLOBIN AND HEMOGLOBIN AT TOLUIDINE BLUE CHEMICALLY MODIFIED ELECTRODE

Electrodeposition of the phenothiazine mediator titrant toluidine blue onto a glassy carbon substrate at an appropriate potential was used to construct a toluidine blue chemically modified electrode (CME) exhibiting electrocatalytic reduction for myoglobin and hemoglobin. The CME catalyzed the hemoprotein electroreduction at the reduction potential of the mediator molecule. When the CME as used as a detector for flow injection analysis at a constant applied potential of -0.30 V vs. a saturated calomel electrode, it gave detection limits of 20 and 50 ng (1.2 and 0.78 pmol) injected myoglobin and hemoglobin, respectively, with a dynamic linear concentration range over 2 orders of magnitude. After a brief equilibration period, the CME retained nearly 90% of its initial myoglobin response over 8 hours of continuous exposure to the flow-through system.

Studies on the regional feature of organic carbon in sediments off the Huanghe River Estuary waters

Organic carbon (OC) in definitely small area sediments(according to marine dimension)off the Huanghe River Estuary is investigated in order to evaluate the feature of regional difference of physical and chemical properties in marginal sea sediments. The distributions of OC in sediments with natural grain size and the relationship with the pH, Eh,Es and Fe3+/Fe2+ are discussed. In addition,OC decomposition rates in surfacial/subsurfacial sediments are estimated. OC concentrations range from 0.26% to 1.8%(wt)in the study area. Significant differences in OC content and in horizontal distribution as well as various trends in surfacial/subsurfacial sediments exhibit the feature of regional difference remarkably in marginal sea sediments. The complicated distribution of OC in surface sediments is due to the influence of bacterial activity and abundance, bioturbation of benthos and physical disturbance. The OC decomposition rate constant in surfacial/subsurfacial sediments ranges from 0.0097 to 0.076 a(-1) and the relatively high values may be mainly related to bacteria that are mainly responsible for OC mineralization;meio-and macrofauna affect OC degradation both directly, through feeding on it, and indirectly through bioturbation and at the same time coarse sediments are also disadvantageous to OC preservation. In almost all the middle and bottom sediments the contents of OC decrease with the increase of deposition depth, which indicates that mineralization of OC in the middle and bottom sediments has occurred via processes like SO42- reduction and Fe-oxide reduction.

Antitumour prodrug development using cytochrome P450 (CYP) mediated activation

An ideal cancer chemotherapeutic prodrug is completely inactive until metabolized by a tumour-specific enzyme, or by an enzyme that is only metabolically competent towards the prodrug under physiological conditions unique to the tumour. Human cancers, including colon, breast, lung, liver, kidney and prostate, are known to express cytochrome P450 (CYP) isoforms including 3A and 1A subfamily members. This raises the possibility that tumour CYP isoforms could be a focus for tumour-specific prodrug activation. Several approaches are reviewed, including identification of prodrugs activated by tumour-specific polymorphic CYPs, use of CYP-gene directed enzyme prodrug therapy and CYPs acting as reductases in hypoxic tumour regions. The last approach is best exemplified by AQ4N, a chemotherapeutic prodrug that is bioreductively activated by CYP3A. This study shows that freshly isolated murine T50/80 mammary carcinoma and RIF-1 fibrosarcoma 4-electron reduces AQ4N to its cytotoxic metabolite, AQ4 (T50/80 K-m = 26.7 mu M, V-max = 0.43 mu M/mg protein/min; RIF-1 K-m = 33.5 mu M, V-max = 0.42 mu M/mg protein/min) via AQM, a mono-N-oxide intermediate (T50/80 K-m = 37.5 mu M; V-max = 1.4 mu M/mg protein/min; RIF-1 K-m = 37.5 mu M; V-max = 1.2 mu M/mg protein/min). The prodrug conversion was dependent on NADPH and inhibited by air or carbon monoxide. Cyp3A mRNA and protein were both present in T50/80 carcinoma grown in vivo (RIF-1 not measured). Exposure of isolated tumour cells to anoxia (2 h) immediately after tumour excision increased cyp3A protein 2-3-fold over a 12 h period, after which time the cyp protein levels returned to the level found under aerobic conditions. Conversely, cyp3A mRNA expression showed an initial 3-fold decrease under both oxic and anoxic conditions; this returned to near basal levels after 8-24 h. These results suggest that cyp3A protein is stabilized in the absence of air, despite a decrease in cyp3A mRNA. Such a 'stabilization factor' may decrease cyp3A protein turnover without affecting the translation efficiency of cyp3A mRNA. Confirmation of the CYP activation of AQ4N bioreduction was shown with human lymphoblastoid cell microsomes transfected with CYP3A4, but not those transfected with CYP2B6 or cytochrome P450 reductase. AQ4N is also reduced to AQ4 in NADPH-fortified human renal cell carcinoma (K-m = 4 mu M, V-max = 3.5 pmol/mg protein/min) and normal kidney (K-m = 4 mu M, V-max = 4.0 pmol/mg protein/min), both previously shown to express CYP3A. Germane to the clinical potential of AQ4N is that although both normal and tumour cells are capable of reducing AQ4N to its cytotoxic species, the process requires low oxygen conditions. Hence, AQ4N metabolism should be restricted to hypoxic tumour cells. The isoform selectivity of AQ4N reduction, in addition to its air sensitivity, indicates that AQ4N haem coordination and subsequent oxygen atom transfer from the active-site-bound AQ4N is the likely mechanism of N-oxide reduction. The apparent increase in CYP3A expression under hypoxia makes this a particularly interesting application of CYPs for tumour-specific prodrug activation.