Polycyclic aromatic hydrocarbon and particulate emissions from two-stage combustion of polystyrene: the effect of the primary furnace temperature

A study is presented on laboratory-scale combustion of polystyrene (PS) to identify staged-combustion conditions that minimize emissions. Batch combustion of shredded PS was conducted in fixed beds placed in a bench-scale electrically heated horizontal muffle furnace. In most cases, combustion of the samples occurred by forming gaseous diffusion flames in atmospheric pressure air. The combustion effluent was mixed with additional air, and it was channeled to a second muffle furnace (afterburner) placed in series. Further reactions took place in the secondary furnace at a residence time of 0.7 s. The gas temperature of the primary furnace was varied in the range of 500-1,000 degrees C, while that of the secondary furnace was kept fixed at 1,000 degrees C. Sampling for CO, CO2, O2, soot, and unburned hydrocarbon emissions (volatile and semivolatile, by GC-MS) was performed at the exits of the two furnaces. Results showed that the temperature of the primary furnace, where PS gasifies, is of paramount importance to the formation and subsequent emissions of organic species and soot. Atthe lowesttemperatures explored, mostly styrene oligomers were identified at the outlet of the primary furnace, but they did not survive the treatment in the secondary furnace. The formation and emission of polycyclic aromatic hydrocarbons (PAH) and soot were suppressed. As the temperature in the first furnace was raised, increasing amounts of a wide range of both unsubstituted and substituted PAH containing up to at least seven condensed aromatic rings were detected. A similar trend was observed for total particulate yields. The secondary furnace treatment reduced the yields of total PAH, but it had an ambiguous effect on individual species. While most low molecular mass PAH were reduced in the secondary furnace, concentrations of some larger PAH increased under certain conditions. Thus, care in the selection of operating conditions of both the primary furnace (gasifier/ burner) and the secondary furnace (afterburner) must be exercised to minimize the emission of hazardous pollutants. The emissions of soot were also reduced in the afterburner but not drastically. This indicates that soot is indeed resistant to oxidation; thus, it would be best to avoid its formation in the first place. An oxidative pyrolysis temperature of PS in the vicinity of 600 degrees C appears to accomplish exactly that. An additional afterburner treatment at a sufficiently high temperature (1,000 degrees C) may be a suitable setting for minimization of most pollutants. To obtain deeper understanding of chemical processes, the experimental results were qualitatively compared with preliminary predictions of a detailed kinetic model that describes formation and destruction pathways of chemical species including most PAH observed in the present work. The modeling was performed forthe secondary furnace assuming plug-flow conditions therein. The experimentally determined chemical composition at the outlet of the primary furnace was part of the input parameters of the model calculation.     

Catalytic deoxygenation of liquid biomass for hydrocarbon fuels

Liquid biomass such as methyl laurate and canola oil is deoxygenated with hydrogen and NiMo/γ-Al₂O₃ catalyst. Oxygen from methyl laurate and canola oil is removed at 18.25–85.13 bar initial cold hydrogen pressure and 300–400 °C, using a 316 stainless steel batch reactor. Removal of oxygen from liquid methyl laurate and canola oil is evaluated with a GC/MS analyzer for liquid reaction products and another GC for gaseous reaction products. The range of reaction duration of liquid biomass in the batch reactor is 30–60 min under the deoxygenation conditions. Conversion of liquid biomass into gaseous products is evaluated with analysis data of gas products and a mass balance in terms of hydrogen.The objective of this research is to develop an efficient method of removing oxygen from liquid biomass to produce petroleum-comparative liquid hydrocarbons with hydrogen and a catalyst.Removal of oxygen from bio-based fuels for liquid hydrocarbon fuel is needed to increase its energy intensity, stability, and decrease its viscosity. In this paper, removal of oxygen from methyl laurate and canola oil is discussed in detail in terms of various oxygen removal conditions such as reaction temperature and pressure, catalyst amount, and hydrodynamics of heterogeneous reaction mixture in the batch reactor.     

Effects of physical-chemical characteristics on the sorption of selected endocrine disruptors by dissolved organic matter surrogates

Sorption coefficients (K(oc) values) of selected endocrine disruptors for a wide variety of dissolved organic matter (DOM) were measured using fluorescence quenching and solubility enhancement. 17beta-Estradiol, estriol, 17alpha-ethynylestradiol, p-nonylphenol, p-tert-octylphenol, and dibutylphthalate were selected as endocrine disruptors. Aldrich humic acid, Suwannee River humic and fulvic acids, Nordic fulvic acid, alginic acid, dextran, and tannic acid were selected as DOM surrogates. The resulting sorption coefficients (log K(oc)) were independent of octanol-water partitioning coefficients (log K(ow)) of the selected endocrine disruptors, indicating the hydrophobic interaction is not the predominant sorption mechanism. Moreover, the K(oc) values for the selected endocrine disruptors, especially the steroid estrogens, correlated much better with UV absorptivity at 272 nm (A272) and phenolic group concentration of the DOM than with either the H/O or the (O+N)/C atomic ratio of the DOM. This suggests that the sorption mechanism is closely related to the interaction between pi-electrons and the hydrogen bonds, i.e., the affinity between phenolic groups of the steroid estrogens and DOM is suggested to provide a relatively large contribution to the overall sorption and yield the K(oc) values of the steroid estrogens as high as those of the alkylphenols and dibutylphthalate, which are suggested to be dominated by nonspecific hydrophobic interaction.     

Mammary epithelial proliferation and estrogen receptor alpha expression in prepubertal heifers: effects of ovariectomy and growth hormone

The objectives of this study were to determine the effects of ovariectomy and growth hormone on mammary epithelial cell proliferation and estrogen receptor alpha (ER alpha) expression within the bovine mammary gland. Two experiments were performed. In the first experiment, eight Holstein heifer calves aged between 1 and 3 mo were ovariectomized, while six calves served as controls. At 6 mo of age, calves were treated with bromodeoxyuridine (BrdU) to label proliferating cells and sacrificed 2 h later. Coinciding with reduced mammary mass (304 +/- 25 vs. 130 +/- 21 g), proliferation of mammary epithelial cells was significantly lower in ovariectomized heifers compared to control heifers (2.24 vs. 0.25%). ER alpha expression was restricted to mammary epithelial cells and was not observed within intra-lobular stroma of parenchymal tissue. The proportion of ER alpha positive cells was significantly higher in ovariectomized heifers than in controls (36.1% +/- 2.2 vs. 46.7% +/- 2.4). In the second experiment, mammary biopsies were taken from five 6-mo-old heifers, immediately preceding and 7 d following a single injection of bovine growth hormone. Mammary epithelial cell proliferation (assessed by incorporation of 3H-thymidine) was increased by growth hormone. The proportion of ER alpha positive mammary epithelial cells was not increased by growth hormone. In conclusion, reduced mammary epithelial cell proliferation following ovariectomy was associated with an increase in ER alpha expression, whereas increased proliferation caused by bovine growth hormone was not associated with changes in the proportion of ER alpha positive cells.     

The impact of river regulation and climate change on the barred estuary of the Oued Massa,southern Morocco

The estuary of the Oued Massa, southern Morocco, has experienced alternating phases of tidal and lagoon conditions. Using field surveys, aerial photographs and rainfall–runoff records the dominant processes and recent evolution of the estuary are described. These data suggest that the character of the estuary has changed since the upstream impoundment of the river by the Youssef Ben Tachfine reservoir. The frequency of low‐flows has been significantly increased by river regulation, as has the mean interval between flood events. Using reconstructed flow series it is speculated that lagoon conditions have become more common in the post‐impoundment era than at any time since the 1920s. Although increases in winter precipitation projected by the global climate model HadCM2 for 2030–2049 imply a higher frequency of flood flows entering the reservoir in the future, the magnitude and frequency of such inflows are still within historic variability. Nonetheless, higher inflows may produce more frequent spills with concomitant bar breaching and termination of lagoon phases. Despite this, it is argued that the presence of the dam is ultimately of greater consequence to the functioning of the estuary–lagoon system than future precipitation changes over the region. Copyright © 2001 John Wiley & Sons, Ltd.     

Effect of lubricating oil contamination on evaporation in refrigerants R12 and R22

An investigation has been made into the effect of oil concentration on evaporation heat transfer coefficients in refrigerant-oil mixtures flowing in a horizontal tube. A new correlation is presented for heat transfer coefficients in convective evaporation of refrigerant-oil mixtures that predicts the results of the present study within approximately ±20%. The paper reports measurements of evaporation heat transfer coefficients in refrigerants R12 and R22, both oil-free and with two concentrations of Shell Clavus 32 oil. A 1·8 m long ⅜ in O/D copper tube (8·05 mm I/D) was used, at evaporation temperatures of −5°C, 0°C and +5°C. Heat flux and mixture mass velocity were kept constant at 2500 W m⁻² and 155 kg m⁻² s⁻¹, respectively, and measured coefficients were in the range of 1400 to 3900 W m⁻² K⁻¹. The results showed that, for a complete evaporator, 2% oil may be expected to increase the heat transfer coefficient by 12%, but 10% oil returns the coefficient to oil-free values.     

Processing and storage effects on monomeric anthocyanins, percent polymeric color, and antioxidant capacity of processed blueberry products

ABSTRACT:  This study evaluated the effects of processing and 6 mo of storage on total monomeric anthocyanins, percent polymeric color, and antioxidant capacity of blueberries that were canned in syrup (CS), canned in water (CW), pureed, and juiced (clarified and nonclarified). Total monomeric anthocyanins, percent polymeric color, and oxygen radical absorbing capacity (ORAC) assay using fluorescein (ORAC_FL) were determined postprocessing after 1 d, and 1, 3, and 6 mo of storage. Thermal processing resulted in marked losses in total anthocyanins (28% to 59%) and ORAC_FL values (43% to 71%) in all products, with the greatest losses occurring in clarified juices and the least in nonclarified juices. Storage at 25 °C for 6 mo resulted in dramatic losses in total anthocyanins, ranging from 62% in berries CW to 85% in clarified juices. This coincided with marked increases in percent polymeric color values of these products over the 6-mo storage. The ORAC_FL values showed little change during storage, indicating that the formation of polymers compensated for the loss of antioxidant capacity due to anthocyanin degradation. Methods are needed to retain anthocyanins in thermally processed blueberries.     

Pressurized liquid extraction of flavonoids from spinach

ABSTRACT:  Pressurized liquid extraction (PLE) using water and a 70:30 mixture of ethanol and water over the temperature range of 50 to 190 °C was used to extract flavonoids from dried spinach. The total phenolic content, antioxidant capacity, color, and browning indices of the extracts were also evaluated. PLE using a 70:30 mixture of ethanol and water was more effective than water in extracting flavonoids from spinach. Flavonoids were effectively extracted over the temperature band of 50 to 130 °C with water and 50 to 150 °C with ethanolic solvent. Levels of total phenolics and ORAC values increased with increasing extraction temperature, indicating that flavonoids were minor contributors to antioxidant capacity at elevated extraction temperatures. Browning of ethanolic extracts correlated highly with ORAC values over the temperature range of 50 to 190 °C, and the ORAC values of the large molecular weight fraction (> 1000 Da) increased linearly over the temperature range, indicating that Maillard polymers were the major contributors to antioxidant capacity. The results illustrate that PLE temperatures of < 130 °C for water or < 150 °C for ethanolic solvent may be used to extract flavonoids, followed by a high temperature (> 170 °C) extraction to generate antioxidant-rich moieties.     

Templated Crosslinked Imidazolyl Acrylate for Electronic Detection of Nitroaromatic Explosives

A low‐voltage operable, highly sensitive, and selectively responsive polymer for the detection of nitroaromatic explosives is investigated. Resistive devices are fabricated by simple spin‐coating on flexible and transparent substrates in addition to silicon substrates and are stable under ambient temperature and oxygen levels before exposure to the nitroaromatics. After exposure to 2,4,6‐trinitrotoluene (TNT), the devices show increased conductance, even with picogram (pg) quantities of TNT, accompanied by a confirming color change from colorless to deep red. The relative conductance increase per unit exposure is the highest yet reported for TNT. Aromatic anion salts, on the other hand, do not induce any electronic responses. ¹H NMR and microscopic analyses show chemical interactions and morphological changes correlated with the electronic responses, some of which are specific to TNT in relation to other nitroaromatics. The binding constant for the imidazole rings and TNT is on the order of tens of M ^?1. The materials are promising for rapid indication of exposure to nitroaromatic compounds.     

Internal short circuit in Li-ion cells

Effects of internal short circuit (ISCr) on thermal stability of Li-ion cells of various sizes (130-1100 mAh) are investigated using a combination of experimental methods and thermal modeling. Three experimental methods were evaluated: small nail penetration, small indentation, and cell pinch test. The small nail penetration and indentation tests created significant heat sinking to the cell-can or to the nail. Only the cell pinch test provided a reasonable approximation of a high risk ISCr event. ISCr location plays a critical role in the consequences of an ISCr event. ISCr at the edge of the electrode is the worst case because of its limited heat conduction to the cell-can. The effects of cell capacity and state of charge on ISCr are also evaluated through tests and thermal modeling.