Development of Thixotropic Coatings Using Dimerized Soybean Oil Fatty Acids: The Case of Polyamide of 1,2-Phenylene Diamine

Soybean oil (SBO) was dimerized and the crude dimer acid product reacted with 1,2-phenylene diamine at 210 ± 5 °C under inert atmosphere to obtain fatty polyamide (FPA). The FPA was used to modify a commercial alkyd resin by reacting a mixture of the alkyd resin with 5 wt% of FPA at 120 °C for 80 min under inert atmosphere. The FTIR spectrum of the FPA modified resin showed evidence of higher degree of H-bonding than was found for the unmodified alkyd. White gloss coatings of 15, 20, 25, and 30% solids were formulated from the modified and unmodified resins and examined for performance with respect to: leveling, sag resistance, drying time, pigment settling, skinning tendency and film hardness. Results showed that the unmodified alkyd coatings exhibited good leveling but poor sag resistance at all solid contents. In contrast, FPA modified alkyd coatings combined good leveling with high sag resistance indicating their thixotropic nature. A strong tendency to pigment settling was observed for unmodified alkyd coatings but was not observed in the FPA modified alkyd coatings. The modified alkyd coatings showed skinning while the unmodified alkyd coatings did not skin. A 30% solids coating formulation of the FPA modified resin showed shorter surface dry time but longer hard dry time than the unmodified alkyd resin coating.     

Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), ¹H and ¹³C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, ¹³C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.     

Preparation and Characterization of Hydrogel Based on Poly(vinyl alcohol) Cross-Linked by Different Cross-Linkers Used to Dry Organic Solvents

Poly(vinyl alcohol) (PVA) hydrogels were chemically cross-linked with/without different cross-linkers such as glutaraldehyde and epichlorohydrin, in the presence of a catalyst, or activator (potassium hydroxide) to produce three types of hydrogels. The structures of PVA and the prepared gel types were determined by FTIR spectroscopy, the mechanical and thermal properties, of these hydrogels were examined. The effects of different pH values and temperatures on the swelling properties of the prepared gels were examined. From the obtained results, it was found that, the low concentration of the cross-linker produced hydrogel with moderate properties, but in absence of the cross-linker, the obtained hydrogel exhibited good properties and can be used as friendly environmentally moisture absorbents from the organic solvents. The insolubility and swelling properties of gels were tested in these solvents. The results indicated that these hydrogels can be used as moisture absorbents and solvent dryers.     

Purification and Properties of Extracellular Poly(3-hydroxybutyrate) Depolymerase Produced by <Emphasis Type="Italic">Aspergillus fumigatus</Emphasis> 202

An extracellular poly(3-hydroxybutyrate) (PHB) depolymerase produced by a thermotolerant fungal soil isolate, Aspergillus fumigatus 202, was purified and characterized. Maximum PHB depolymerase production was obtained at the end of 48 h with initial medium pH 7.0 and 45 °C in Bushnell Haas Minerals medium containing PHB as sole source of carbon. The PHB depolymerase was purified using size exclusion chromatography to a fold purification of 20.62 and 61.62% yield. SDS-PAGE and isoelectric focusing revealed the molecular weight and pI of the purified enzyme as 63,744 Da and 4.2, respectively. N-terminal amino acid sequence of purified enzyme was HAXDAYLVK. This non-glycosylated enzyme was most active at pH 9.0 and 45 °C. Purified enzyme was inactivated by N-bromosuccinimide and dithiothreitol suggesting the involvement of tryptophan residues and disulfide bonds at its active site. Nonionic detergents like Tween 20, Tween 80 and Triton X-100 inhibited the enzyme activity. Ions like Ca⁺² and Mg⁺² (5 mM) increased the enzyme activity 1.5 times. Fe⁺² effectively inhibited the enzyme activity to 88% whereas Hg⁺² completely inhibited the enzyme.     

Reclaimed Mineland Curve Number Response to Temporal Distribution of Rainfall1

Warner, Richard C., Carmen T. Agouridis, Page T. Vingralek, and Alex W. Fogle, 2010. Reclaimed Mineland Curve Number Response to Temporal Distribution of Rainfall. Journal of the American Water Resources Association (JAWRA) 46(4): 724-732. DOI: 10.1111/j.1752-1688.2010.00444.x Abstract: The curve number (CN) method is a common technique to estimate runoff volume, and it is widely used in coal mining operations such as those in the Appalachian region of Kentucky. However, very little CN data are available for watersheds disturbed by surface mining and then reclaimed using traditional techniques. Furthermore, as the CN method does not readily account for variations in infiltration rates due to varying rainfall distributions, the selection of a single CN value to encompass all temporal rainfall distributions could lead engineers to substantially under- or over-size water detention structures used in mining operations or other land uses such as development. Using rainfall and runoff data from a surface coal mine located in the Cumberland Plateau of eastern Kentucky, CNs were computed for conventionally reclaimed lands. The effects of temporal rainfall distributions on CNs was also examined by classifying storms as intense, steady, multi-interval intense, or multi-interval steady. Results indicate that CNs for such reclaimed lands ranged from 62 to 94 with a mean value of 85. Temporal rainfall distributions were also shown to significantly affect CN values with intense storms having significantly higher CNs than multi-interval storms. These results indicate that a period of recovery is present between rainfall bursts of a multi-interval storm that allows depressional storage and infiltration rates to rebound.     

Prymnesium parvum: The Texas Experience1

Southard, Gregory M., Loraine T. Fries, and Aaron Barkoh, 2010. Prymnesium parvum: The Texas Experience. Journal of the American Water Resources Association (JAWRA) 46(1):14-23. DOI: 10.1111/j.1752-1688.2009.00387.x Abstract: Golden alga Prymnesium parvum was first identified in Texas during a fish kill investigation on the Pecos River in 1985. Since then golden alga kills occurred sporadically in a variety of waters in the western part of the state until 2001 when the alga became endemic in the Brazos, Canadian, Colorado, Red, and Rio Grande river systems, including the water supplies of two public fish hatcheries, the Possum Kingdom and Dundee state fish hatcheries. The increasing area adversely affected by the alga and frequent massive fish kills heightened public and political awareness and concerns regarding the ecological and economic impacts of P. parvum blooms. The Texas Parks and Wildlife Department (TPWD), the wildlife conservation agency of the state, responded to these concerns with a program to assess the ecological and economic impacts and to develop management options. To date 33 water bodies have been affected and losses are conservatively estimated at 34 million fish valued at US$13 million. Several sport fisheries, including smallmouth bass Micropterus dolomieu, striped bass Morone saxatilis, channel catfish Ictalurus punctatus, and blue catfish Ictalurus furcatus, have been severely affected. Additionally, 26 imperiled fish species occur in the affected water basins and some have been adversely affected. Economic losses associated with reduced fishing and other water-based recreational activities appear considerable. The combined economic losses to three counties (Palo Pinto, Stephens, and Young) surrounding Possum Kingdom reservoir for 2001 and 2003 were estimated at US$2.8 million and US$1.1 million, respectively. This paper describes how the TPWD responded to public and political concerns relative to the emergence of golden alga, its harmful effects to fisheries, and its historic and current statewide distribution.     

Simulating the fine and coarse inorganic particulate matter concentrations in a polluted megacity

A three dimensional chemical transport model (PMCAMx) is applied to the Mexico City Metropolitan Area (MCMA) in order to simulate the chemical composition and mass of the major PM₁ (fine) and PM_1–10 (coarse) inorganic components and determine the effect of mineral dust on their formation. The aerosol thermodynamic model ISORROPIA-II is used to explicitly simulate the effect of Ca, Mg, and K from dust on semi-volatile partitioning and water uptake. The hybrid approach is applied to simulate the inorganic components, assuming that the smallest particles are in thermodynamic equilibrium, while describing the mass transfer to and from the larger ones. The official MCMA 2004 emissions inventory with improved dust and NaCl emissions is used. The comparison between the model predictions and measurements during a week of April of 2003 at Centro Nacional de Investigacion y Capacitacion Ambiental (CENICA) “Supersite” shows that the model reproduces reasonably well the fine mode composition and its diurnal variation. Sulfate predicted levels are relatively uniform in the area (approximately 3 μg m^?3), while ammonium nitrate peaks in Mexico City (approximately 7 μg m^?3) and its concentration rapidly decreases due to dilution and evaporation away from the urban area. In areas of high dust concentrations, the associated alkalinity is predicted to increase the concentration of nitrate, chloride and ammonium in the coarse mode by up to 2 μg m^?3 (a factor of 10), 0.4 μg m^?3, and 0.6 μg m^?3 (75%), respectively. The predicted ammonium nitrate levels inside Mexico City for this period are sensitive to the physical state (solid versus liquid) of the particles during periods with RH less than 50%.     

Using a reduced Common Representative Intermediates (CRIv2-R5) mechanism to simulate tropospheric ozone in a 3-D Lagrangian chemistry transport model

A reduced chemical scheme (CRIv2-R5) which describes ozone formation from the tropospheric degradation of methane and 22 emitted non-methane hydrocarbons and oxygenated volatile organic compounds has been applied in a global-3D chemistry transport model (STOCHEM). The scheme, which contains 220 species in 609 reactions, has been used to simulate ozone and its precursors for the meteorological year of 1998 and the results have been compared with those from STOCHEM runs with its original chemistry. Compared with the original chemistry scheme, the degradation of a larger number of more reactive VOCs in the CRI scheme results in the formation (and their consequent transportation) of more NO_x active reservoirs thus leading to formation of more ozone away from land-based sources. Conversely, the more reactive VOCs also lead to greater removal of OH in continental areas and greater formation of OH in marine environments. STOCHEM run with the CRI scheme simulates more ozone (by up to 10 ppb), which results in better agreement with observed vertical ozone profiles. The CRI scheme transforms the globally and annually integrated ozone budget for the considered year in STOCHEM from a net loss of ?55 Tg yr^?1 to a net gain of +50 Tg yr^?1.     

A new condensed toluene mechanism for Carbon Bond: CB05-TU

Toluene is ubiquitous in urban atmospheres and is a precursor to tropospheric ozone and aerosol (smog). An important characteristic of toluene chemistry is the tendency of some degradation products (e.g., cresols and methyl-catechols) to form organic nitro and nitrate compounds that sequester NOx (NO and NO₂) from active participation in smog formation. Explaining the NOx sinks in toluene degradation has made mechanism development more difficult for toluene than for many other organic compounds. Another challenge for toluene is explaining sources of radicals early in the degradation process. This paper describes the development of a new condensed toluene mechanism consisting of 26 reactions, and evaluates the performance of CB05 with this new toluene scheme (Toluene Update, TU) against 38 chamber experiments at 7 different environmental chambers, and provides recommendations for future developments. CB05 with the current toluene mechanism (CB05-Base) under-predicted the maximum O₃ and O₃ production rate for many of these toluene–NOx chamber experiments, especially under low-NOx conditions ([NOx]_t=0 < 100 ppb). CB05 with the new toluene mechanism (CB05-TU) includes changes to the yields and reactions of cresols and ring-opening products, and showed better performance than CB05-Base in predicting the maximum O₃, O₃ formation rate, NOx removal rate and cresol concentration. Additional environmental chamber simulations with xylene–NOx experiments showed that the TU mechanism updates tended to improve mechanism performance for xylene.