Modeling the Effect of Vapor Wall Deposition on the Formation of Secondary Organic Aerosol in Chamber Studies

Laboratory chamber experiments are used to investigate formation of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors under a variety of environmental conditions. Simulations of these experiments test our understanding of the prevailing chemistry of SOA formation as well as the dynamic processes occurring in the chamber itself. One dynamic process occurring in the chamber that was only recently recognized is the deposition of vapor species to the Teflon walls of the chamber. Low-volatility products formed from the oxidation of volatile organic compounds (VOCs) deposit on the walls rather than forming SOA, decreasing the amount of SOA formed (quantified as the SOA yield: mass of SOA formed per mass of VOC reacted). In this work, several modeling studies are presented that address the effect of vapor wall deposition on SOA formation in chambers.

A coupled vapor-particle dynamics model is used to examine the competition among the rates of gas-phase oxidation to low volatility products, wall deposition of these products, and mass transfer to the particle phase. The relative time scales of these rates control the amount of SOA formed by affecting the influence of vapor wall deposition. Simulations show that an effect on SOA yield of changing the vapor-particle mass transfer rate is only observed when SOA formation is kinetically limited. For systems with kinetically limited SOA formation, increasing the rate of vapor-particle mass transfer by increasing the concentration of seed particles is an effective way to minimize the effect of vapor wall deposition.

This coupled vapor-particle dynamics model is then applied to α-pinene ozonolysis SOA experiments. Experiments show that the SOA yield is affected when changing the oxidation rate but not when changing the rate of gas-particle mass transfer by changing the concentration of seed particles. Model simulations show that the absence of an effect of changing the seed particle concentration is consistent with SOA formation being governed by quasi-equilibrium growth, in which gas-particle equilibrium is established much faster than the rate of change of the gas-phase concentration. The observed effect of oxidation rate on SOA yield arises due to the presence of vapor wall deposition: gas-phase oxidation products are produced more quickly and condense preferentially onto seed particles before being lost to the walls. Therefore, for α-pinene ozonolysis, increasing the oxidation rate is the most effective way to mitigate the influence of vapor wall deposition.

Finally, the detailed model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to simulate α-pinene photooxidation SOA experiments. Unexpectedly, α-pinene OH oxidation experiments show no effect when changing either the oxidation rate or the vapor-particle mass transfer rate, whereas GECKO-A predicts that changing the oxidation rate should drastically affect the SOA yield. Sensitivity studies show that the assumed magnitude of the vapor wall deposition rate can greatly affect conclusions drawn from comparisons between simulations and experiments. If vapor wall loss in the Caltech chamber is of order 10^-5 s^-1, GECKO-A greatly overpredicts SOA during high UV experiments, likely due to an overprediction of second-generation products. However, if instead vapor wall loss in the Caltech chamber is of order 10^-3 s^-1, GECKO-A greatly underpredicts SOA during low UV experiments, possibly due to missing autoxidation pathways in the α-pinene mechanism.

Effect of gamma-irradiation on total organic carbon and trihalomethane formation potential

This research was conducted to study the use of radiation in water treatment as an alternative to chlorination which has caused health concerns due to the formation of harmful disinfection by-products. Groundwater solutions from the Biscayne aquifer were radiated with Cobalt-60 gamma radiation and studied for changes in dissolved organic carbon (DOC), UV absorbance at 254 nm (UV254), fluorescence and trihalomethane formation potential (THMFP). Molecular fractionations were conducted by ultrafiltration. Effect of the combination of radiation/peroxide was studied for DOC and UV254. Radiation showed significant removal in DOC and THMFP. Similar results were seen in the fluorescence and UV absorbance experiments. Radiation/peroxide did not improve the DOC removal. Radiation of the groundwater samples broke the larger molecular weight fractions in to smaller fractions.

Effect of sonic and ultrasonic activation on organic tissue dissolution from simulated grooves in root canals using sodium hypochlorite and EDTA

Aim: To compare soft-tissue dissolution by sodium hypochlorite, with an EDTA intermediate rinse, with or without activation with passive ultrasonic activation (PUI) or sonic activation using the Endoactivator (EA) or Eddy tips (ED). Methodology: The root canals of eighty-three human maxillary central incisors were chemo-mechanically prepared and the teeth split. A standardized longitudinal intracanal groove was created in one of the root halves. Eighty-three porcine palatal mucosa samples were collected, adapted to fit into the grooves and weighed. The re-assembled specimens were randomly divided into four experimental groups (n = 20), based on the final rinse: no activation; EA; PUI; ED, using 2.5% sodium hypochlorite, with an EDTA intermediate rinse. A control group (n = 3) was irrigated with distilled water without activation. The solutions were delivered using a syringe and needle 2 mm from working length. Total irrigation time was 150 s, including 60 s of activation in the specific groups. The study was carried out at 36 ± 2 °C. The porcine palatal mucosa samples were weighed after completion of the assays. Student paired t-test and anova were used to assess the intra- and intergroup weight changes. The multiple comparisons were evaluated using Bonferroni correction (α = 0.05). Results: Weight loss occurred in all experimental groups. Irrigant activation resulted in greater weight loss when compared to the nonactivated group [vs. EA (P = 0.001); vs. PUI (P < 0.001); vs. ED (P < 0.001)]. No significant differences were found amongst the different activation systems. Conclusions: Activation increased the tissue-dissolving activity of irrigants from artificial grooves in root canals of maxillary central incisors. © 2016 International Endodontic Journal. Published by John Wiley & Sons Ltd.

Degradation and sorption of fipronil and atrazine in Latossols with organic residues from sugarcane crop.

ABSTRACT: Organic residues from sugarcane crop and processing (vinasse, boiler ash, cake filter, and straw) are commonly applied or left on the soil to enhance its fertility. However, they can influence pesticide degradation and sorption. The objective of this study was to assess the effect of adding these organic residues on the degradation and sorption of fipronil and atrazine in two soils of the State of Mato Grosso do Sul, MS, Brazil. The degradation experiment was carried out with laboratory-incubated (40 days; 28°C; 70% field capacity) soils (0-10cm). The batch equilibration method was used to determine sorption. Fipronil (half-life values of 15-105 days) showed to be more persistent than atrazine (7-17 days). Vinasse application to the soil favored fipronil and atrazine degradation, whereas cake filter application decreased the degradation rates for both pesticides. Values for sorption coefficients (Kd) were determined for fipronil (5.1-13.2mL g-1) and atrazine (0.5-1.5mL g-1). Only straw and cake filter residues enhanced fipronil sorption when added to the soil, whereas all sugarcane residues increased atrazine sorption. RESUMO: Resíduos orgânicos do cultivo e processamento da cana-de-açúcar (vinhaça, cinzas, torta de filtro e palha) são usualmente aplicados ou deixados no solo para aumentar sua fertilidade, mas eles podem influenciar na degradação e sorção de agrotóxicos. O objetivo deste estudo foi avaliar o efeito da adição desses resíduos orgânicos no solo sobre a degradação e sorção do fipronil e da atrazina em dois solos no Estado de Mato Grosso do Sul, MS, Brasil. O experimento de degradação foi realizado com solos (0-10cm) incubados em laboratório (40 dias; 28°C; 70% da capacidade de campo). Para determinar a sorção, foi usado o método da batelada. Fipronil mostrou ser mais persistente (valores de meia-vida entre 15-105 dias) que atrazina (7-17 dias). O solo com adição de vinhaça favoreceu a degradação de fipronil e atrazina, enquanto adição da torta de filtro desacelerou o processo. Os valores do coeficiente de sorção (Kd) foram determinados para fipronil (5,1-13,2mL g-1) e atrazina (0,5-1,5mL g-1). Apenas os resíduos palha e torta de filtro aumentaram a sorção de fipronil quando adicionados ao solo, enquanto todos os resíduos aumentaram a sorção de atrazina.

The Effect of Coconut Oil and Hibiscus Rosasinensis on Ration Degradability and Number of Protozoa

Concentrated diet based on rice bran 69%, coconut meal 30%, urea 1% and field grass (fg), parsial defaunation agent Hibiscus rosasinensis (Hr) and coconut oil (Co) was used in propotion 37,5% fg + 2,5% Hr; 35% fg + 5% Hr; 37,5% fg + 2,5% Co and 35% + 5% Co. the feed of concentrate and feed grass 60 : 40 % are evaluated in vitro for dry matter degradability (DMD), organic matter degradability (OMD) and number of protozoa (NP). Variance analysis and orthogonal contrast was applied according to Steel and Torrie (1981). The result show that defaunation agent Hr and Co 2,5% and 5% increased (P< 0.01) DMD in the order 60.20; 59.40; 56.60 and 55.60 respectively, compare with no defaunation agent (54,60%). It also increased OMD 62.20%; 60.40; 58.40 and 57.20% compare with no agent (56.40%). While number of protozoa decreased (P< 0.01) 2.456; 2.316; 2.396 and 2.286 x 104/ml rumen liquid compare with no defaunation agent (2.564 x 104/ml rumen liquid). (Animal Production 2(2): 53-59 (2000) Key words : Hibiscus rosasinensis, digestibility, and number of protozoa

Organic and acquisitive employment growth : re-examining,testing and extending Penrose's Growth Theory.

Edith Penrose’s theory of firm growth postulates that a firm’s current growth rate will be influenced by the adjustment costs of, and changes to a firm’s productive opportunity set arising from, previous growth. Although she explicitly considered the impact of previous organic growth on current organic growth, she was largely silent about the impact of previous acquisitive growth. In this paper we extend Penrose’s work to examine that the relative impact of organic and acquisitive growth on the adjustment costs and productive opportunity set of the firm. Employing a panel of commercially active enterprises in Sweden over a 10 year period our results suggest the following. First, previous organic growth acts as a constraint on current organic growth. Second, previous acquisitive growth has a positive effect on current organic growth. We conclude that organic growth and acquisitive growth constitute two distinct strategic options facing the firm, which have a differential impact on the future organic growth of the firm.

Effect of orthokeratology on peripheral aberrations of the eye

Purpose: To investigate the effect of orthokeratology on peripheral aberrations in two myopic volunteers. Methods: The subjects wore reverse geometry orthokeratology lenses overnight and were monitored for 2 weeks of wear. They underwent corneal topography, peripheral refraction (out to ±34° along the horizontal visual field) and peripheral aberration measurements across the 42° × 32° central visual field using a modified Hartmann-Shack aberrometer. Results: Spherical equivalent refraction was corrected for the central 25° of the visual fields beyond which it gradually returned to its preorthokeratology values. There were increases in axial coma, spherical aberration, higher order root mean square aberrations, and total root-mean-squared aberrations (excluding defocus). The rates of change of vertical and horizontal coma across the field changed in sign. Total root mean square aberrations showed a quadratic rate of change across the visual field which was greater subsequent to orthokeratology. Conclusion: Although orthokeratology can correct peripheral relative hypermetropia it induces dramatic increases in higher-order aberrations across the field

Numerical and experimental investigation of wedge tip radius effect on wedge plasmons

We report numerical analysis and experimental observation of strongly localized plasmons guided by triangular metal wedges and pay special attention to the effect of smooth (nonzero radius) tips. Dispersion, dissipation, and field structure of such wedge plasmons are analyzed using the compact two-dimensional finite-difference time-domain algorithm. Experimental observation is conducted by the end-fire excitation and near-field scanning optical microscope detection of the predicted plasmons on 40°silver nanowedges with the wedge tip radii of 20, 85, and 125 nm that were fabricated by the focused-ion beam method. The effect of smoothing wedge tips is shown to be similar to that of increasing wedge angle. Increasing wedge angle or wedge tip radius results in increasing propagation distance at the same time as decreasing field localization (decreasing wave number). Quantitative differences between the theoretical and experimental propagation distances are suggested to be due to a contribution of scattered bulk and surface waves near the excitation region as well as the addition of losses due to surface roughness. The theoretical and measured propagation distances are several plasmon wavelengths and are useful for a range of nano-optical applications

Effect of optical aberrations on the colour appearance of small lights

Purpose: Small red lights (one minute of arc or less) change colour appearance with positive defocus. We investigated the influence of longitudinal chromatic aberration and monochromatic aberrations on the colour appearance of small narrow band lights. Methods: Seven cyclopleged, trichromatic observers viewed a small light (one minute of arc, λmax = 510, 532, 550, 589, 620, 628 nm, approximately 19 per cent Weber contrast) centred within a black annulus (4.5 minutes of arc) and surrounded by a uniform white field (2,170 cd/m2). Pupil size was four millimetres. An optical trombone varied focus. Longitudinal chromatic aberration was controlled with a two component Powell achromatising lens that neutralises the eye’s chromatic aberration; a doublet that doubles and a triplet that reverses the eye’s chromatic aberration. Astigmatism and higher order monochromatic aberrations were corrected using adaptive optics. Results: Observers reported a change in appearance of the small red light (628 nm) without the Powell lens at +0.49 ± 0.21 D defocus and with the doublet at +0.62 ± 0.16 D. Appearance did not alter with the Powell lens, and five of seven observers reported the phenomenon with the triplet for negative defocus (-0.80 ± 0.47 D). Correction of aberrations did not significantly affect the magnitude at which the appearance of the red light changed (+0.44 ± 0.18 D without correction; +0.46 ± 0.16 D with correction). The change in colour appearance with defocus extended to other wavelengths (λmax = 510 to 620 nm), with directions of effects being reversed for short wavelengths relative to long wavelengths. Conclusions: Longitudinal chromatic aberrations but not monochromatic aberrations are involved in changing the appearance of small lights with defocus.

Temperature and electric field dependent mobility in poly„3-hexylthiophene diodes

Current-voltage (I-V) curves of Poly(3-hexyl-thiophene) (P3HT) diodes have been collected to investigate the polymer hole-dominated charge transport. At room temperature and at low electric fields the I-V characteristic is purely Ohmic whereas at medium-high electric fields, experimental data shows that the hole transport is Trap Dominated - Space Charge Limited Current (TD-SCLC). In this regime, it is possible to extract the I-V characteristic of the P3HT/Al junction showing the ideal Schottky diode behaviour over five orders of magnitude. At high-applied electric fields, holes’ transport is found to be in the trap free SCLC regime. We have measured and modelled in this regime the holes’ mobility to evaluate its dependence from the electric field applied and the temperature of the device.

Nitrogen and phosphorus transformations in fixed-film biofilters subjected to aeration/no-aeration cycles

Despite recent developments in fixed-film combined biological nutrients removal (BNR) technology; fixed-film systems (i.e., biofilters), are still at the early stages of development and their application has been limited to a few laboratory-scale experiments. Achieving enhanced biological phosphorus removal in fixed-film systems requires exposing the micro-organisms and the waste stream to alternating anaerobic/aerobic or anaerobic/anoxic conditions in cycles. The concept of cycle duration (CD) as a process control parameter is unique to fixed-film BNR systems, has not been previously investigated, and can be used to optimise the performance of such systems. The CD refers to the elapsed time before the biomass is re-exposed to the same environmental conditions in cycles. Fixed-film systems offer many advantages over suspended growth systems such as reduced operating costs, simplicity of operation, absence of sludge recycling problems, and compactness. The control of nutrient discharges to water bodies, improves water quality, fish production, and allow water reuse. The main objective of this study was to develop a fundamental understanding of the effect of CD on the transformations of nutrients in fixed-film biofilter systems subjected to alternating aeration I no-aeration cycles A fixed-film biofilter system consisting of three up-flow biofilters connected in series was developed and tested. The first and third biofilters were operated in a cyclic mode in which the biomass was subjected to aeration/no-aeration cycles. The influent wastewater was simulated aquaculture whose composition was based on actual water quality parameters of aquacuture wastewater from a prawn grow-out facility. The influent contained 8.5 - 9:3 mg!L a111monia-N, 8.5- 8.7 mg/L phosphate-P, and 45- 50 mg!L acetate. Two independent studies were conducted at two biofiltration rates to evaluate and confirm the effect of CD on nutrient transformations in the biofilter system for application in aquaculture: A third study was conducted to enhance denitrification in the system using an external carbon- source at a rate varying from 0-24 ml/min. The CD was varied in the range of0.25- 120 hours for the first two studies and fixed at 12 hours for the third study. This study identified the CD as an important process control parameter that can be used to optimise the performance of full-scale fixed-film systems for BNR which represents a novel contribution in this field of research. The CD resulted in environmental conditions that inhibited or enhanced nutrient transformations. The effect of CD on BNR in fixed-film systems in terms of phosphorus biomass saturation and depletion has been established. Short CDs did not permit the establishment of anaerobic activity in the un-aerated biofilter and, thus, inhibited phosphorus release. Long CDs resulted in extended anaerobic activity and, thus, resulted in active phosphorus release. Long CDs, however, resulted in depleting the biomass phosphorus reservoir in the releasing biofilter and saturating the biomass phosphorus reservoir in the up-taking biofilter in the cycle. This phosphorus biomass saturation/depletion phenomenon imposes a practical limit on how short or long the CD can be. The length of the CD should be somewhere just before saturation or depletion occur and for the system tested, the optimal CD was 12 hours for the biofiltration rates tested. The system achieved limited net phosphorus removal due to the limited sludge wasting and lack of external carbon supply during phosphorus uptake. The phosphorus saturation and depletion reflected the need to extract phosphorus from the phosphorus-rich micro-organisms, for example, through back-washing. The major challenges of achieving phosphorus removal in the system included: (I) overcoming the deterioration in the performance of the system during the transition period following the start of each new cycle; and (2) wasting excess phosphorus-saturated biomass following the aeration cycle. Denitrification occurred in poorly aerated sections of the third biofilter and generally declined as the CD increased and as the time progressed in the individual cycle. Denitrification and phosphorus uptake were supplied by an internal organic carbon source, and the addition of an external carbon source (acetate) to the third biofilter resulted in improved denitrification efficiency in the system from 18.4 without supplemental carbon to 88.7% when the carbon dose reached 24 mL/min The removal of TOC and nitrification improved as the CD increased, as a result of the reduction in the frequency of transition periods between the cycles. A conceptual design of an effective fixed-film BNR biofilter system for the treatment of the influent simulated aquaculture wastewater was proposed based on the findings of the study.

A comparative study of the effect of calibration conditions on the water equivalence of a range of gel dosimeters

Gel dosimeters are of increasing interest in the field of radiation oncology as the only truly three-dimensional integrating radiation dosimeter. There are a range of ferrous-sulphate and polymer gel dosimeters. To be of use, they must be water-equivalent. On their own, this relates to their radiological properties as determined by their composition. In the context of calibration of gel dosimeters, there is the added complexity of the calibration geometry; the presence of containment vessels may influence the dose absorbed. Five such methods of calibration are modelled here using the Monte Carlo method. It is found that the Fricke gel best matches water for most of the calibration methods, and that the best calibration method involves the use of a large tub into which multiple fields of different dose are directed. The least accurate calibration method involves the use of a long test tube along which a depth dose curve yields multiple calibration points.

A comparative study of the effect of calibration conditions on the water equivalence of a range of gel dosimeters

Gel dosimeters are of increasing interest in the field of radiation oncology as the only truly three-dimensional integrating radiation dosimeter. There are a range of ferrous-sulphate and polymer gel dosimeters. To be of use, they must be water-equivalent. On their own, this relates to their radiological properties as determined by their composition. In the context of calibration of gel dosimeters, there is the added complexity of the calibration geometry; the presence of containment vessels may influence the dose absorbed. Five such methods of calibration are modelled here using the Monte Carlo method. It is found that the Fricke gel best matches water for most of the calibration methods, and that the best calibration method involves the use of a large tub into which multiple fields of different dose are directed. The least accurate calibration method involves the use of a long test tube along which a depth dose curve yields multiple calibration points.