Evaporation rates and vapor pressures of individual aerosol species formed in the atmospheric oxidation of alpha- and beta-pinene

The semivolatile oxidation products (trans-norpinic acid, pinic acid, cis-pinonic acid, etc.) of the biogenic monoterpenes (alpha-pinene, beta-pinene, etc.) contribute to the atmospheric burden of particulate matter. Using the tandem differential mobility analysis (TDMA) technique evaporation rates of glutaric acid, trans-norpinic acid, and pinic acid particles were measured in a laminar flow reactor. The vapor pressure of glutaric acid was found to be log(p0 glutaric/Pa) = - 3,510 K/T + 8.647 over the temperature range 290-300 K in good agreement with the values previously reported by Tao and McMurry (1989). The measured vapor pressure of trans-norpinic acid over the temperature range 290-312 K is log(p0 norpinic/Pa) = - 2,196.9 K/T + 3.522, and the vapor pressure of pinic acid is log(p0 pinic/ Pa) = - 5,691.7 K/T + 14.73 over the temperature range 290-323 K. The uncertainty on the reported vapor pressures is estimated to be approximately +/- 50%. The vapor pressure of cis-pinonic acid is estimated to be of the order of 7 x 10(-5) Pa at 296 K.     

Formation of secondary organic aerosol by reactive condensation of furandiones, aldehydes, and water vapor onto inorganic aerosol seed particles

Volatile furandiones and aldehydes are significant atmospheric oxidation products of aromatic compounds. The mechanism of secondary organic aerosol formation by these compounds was probed using particle chamber observations and macroscale simulations of condensed phases. Growth of inorganic seed aerosol was monitored in the presence of humidity and high concentrations of 2,5-furandione (maleic anhydride), 3-methyl-2,5-furandione (citraconic anhydride), benzaldehyde, and trans-cinnamaldehyde. Particle growth commenced when the gas-phase saturation level of each organic compound and water vapor (relative to its pure liquid), when summed together, reached a threshold near one, implying the formation of a nearly ideal mixed organic/aqueous phase. However, these organics are immiscible with water at the high mole fractions that would be expected in such a phase. Highly acidic dicarboxylic acids produced by the reactions between furandiones and water were shown to rapidly acidify an aqueous phase, resulting in greatly increased benzaldehyde solubility. Thus, the uptake of these organics onto particles in the presence of humidity appears to be reaction-dependent. Finally, it is shown that dicarboxylic acids produced in these reactions recyclize back to furandiones when subjected to normal GC injector temperatures, which could cause large artifacts in gas/particle phase distribution measurements.     

Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer

The Aerodyne aerosol mass spectrometer (AMS) was used to characterize physical and chemical properties of secondary organic aerosol (SOA) formed during ozonolysis of cycloalkenes and biogenic hydrocarbons and photo-oxidation of m-xylene. Comparison of mass and volume distributions from the AMS and differential mobility analyzers yielded estimates of "effective" density of the SOA in the range of 0.64-1.45 g/cm3, depending on the particular system. Increased contribution of the fragment at m/z 44, C02+ ion fragment of oxygenated organics, and higher "delta" values, based on ion series analysis of the mass spectra, in nucleation experiments of cycloalkenes suggest greater contribution of more oxygenated molecules to the SOA as compared to those formed under seeded experiments. Dominant negative "delta" values of SOA formed during ozonolysis of biogenics indicates the presence of terpene derivative structures or cyclic or unsaturated oxygenated compounds in the SOA. Evidence of acid-catalyzed heterogeneous chemistry, characterized by greater contribution of higher molecular weight fragments to the SOA and corresponding changes in "delta" patterns, is observed in the ozonolysis of alpha-pinene. Mass spectra of SOA formed during photooxidation of m-xylene exhibit features consistent with the presence of furandione compounds and nitro organics. This study demonstrates that mixtures of SOA compounds produced from similar precursors result in broadly similar AMS mass spectra. Thus, fragmentation patterns observed for biogenic versus anthropogenic SOA may be useful in determining the sources of ambient SOA.     

Fenton-mediated oxidation in the presence and absence of oxygen

The increased use of Fenton systems for the treatment of contaminated waters and wastewaters necessitates the development of kinetic models capable of accurately simulating key species concentrations in order to optimize system performance and efficiency. In this work a reaction mechanism in which the hydroxyl radical is nominated to be the active oxidant in Fenton systems is used to describe the oxidation of formic acid (HCOOH) under a variety of experimental conditions. A kinetic model based on this reaction mechanism is shown to adequately describe results of experiments in which starting concentrations of H202 and HCOOH varied over 1 and 4 orders of magnitude, respectively, under both air-saturated and deaerated conditions. The intermediate generated during HCOOH oxidation was observed to increase oxidation efficiency, especially at high initial organic concentrations [relative to Fe(II)], by assisting in the redox cycling of iron. In the presence of oxygen, however, such improvement was attenuated through competition for the organic intermediates. While mechanistic analysis and associated kinetic modeling is invaluable in optimization of Fenton systems, a clear understanding of reaction byproducts and their reactivity toward other species in the system is critical for accurate simulations.     

Thirdhand smoke: heterogeneous oxidation of nicotine and secondary aerosol formation in the indoor environment

Tobacco smoking is well-known as a significant source of primary indoor air pollutants. However, only recently has thirdhand smoke (THS) been recognized as a contributor to indoor pollution due to the role of indoor surfaces. Here, the effects of relative humidity (<10% RH and ～ 45% RH) and substrate (cellulose, cotton, and paper) on secondary organic aerosol (SOA) formation from nicotine-ozone-NO(x) reactions are discussed. SOA formation from the sorbed nicotine-ozone reaction ([O(3)] = 55 ppb) varied in size distribution and number, depending on RH and substrate type, indicating the role of substrate and water interactions in SOA formation. This led to SOA yields from cellulose sorbed nicotine-ozone reaction of ～ 1 and 2% for wet and dry conditions, respectively. SOA formation from nicotine-NO(x) reactions was not distinguishable from background levels. Simultaneously, cellulose sorbed nicotine-ozone reaction kinetics ([O(3)] = 55 ppb) were obtained and revealed pseudofirst-order surface rate constants of k(1) = (1 ± 0. 5) × 10(-3) and k(1) < 10(-4) min(-1) under <10% and ～ 45% RH, respectively. Given the toxicity of some of the identified products and that small particles may contribute to adverse health effects, the present study indicates that exposure to THS ozonation products may pose additional health risks.     

Effect of reduced irrigation on growth,yield, ripening rates and water relations of Chardonnay vines grafted to five rootstocks

Background and Aims: In the first decade of the 21st century, drought within the Murray–Darling Basin has reduced the amount of water available for irrigation. We investigated whether the response of vines to reduced irrigation was modified by rootstock. Methods and Results: Reduced irrigation (5 versus 8 ML/(ha·year)) was applied to Chardonnay vines grafted to five rootstocks (Ramsey, 140 Ruggeri, 1103 Paulsen, 110 Richter and K51‐40) for four seasons. It decreased the yield from 29.3 to 26.7 kg/vine, and increased the irrigation water use index (IWUI) from 4.7 to 6.6 t/(ha·ML), but gains in this index declined as the trial progressed. The values of mid‐afternoon leaf water potential were not affected by reduced irrigation, but leaf CO₂ assimilation declined from 13.1 to 11.7 µmol/(m²·s). These effects were independent of rootstock. Reduced irrigation did not increase soil salinity (ECe) or vine tissue Na and Cl concentrations. Vines on Ramsey and 1103 Paulsen rootstocks had higher yields, 32.2 and 30.0 kg/vine, respectively, and the highest IWUIs, 5.9 and 5.5 t/(ha·ML). In two of the three seasons, reducing irrigation did not affect the rates of ripening (°Brix/growing degree days) excepting vines on 1103 Paulsen. Ripening rates varied by 1.5‐fold between seasons. Conclusion: The yield and growth responses of Chardonnay vines to a 35% reduction in irrigation were not modified by rootstock. Significance of the Study: Reducing irrigation did not lead to a build‐up of soil salts. The response of vines to reduced irrigation on rootstocks rated as having good drought tolerance was the same as that for vines on a rootstock rated as having poor drought tolerance.     

Genetic correlations among progeny groups for type traits, milk yield, yield persistency, and culling rates

Associations among six primipara type traits and first and second lactation milk yield, yield persistency, and culling rates were estimated by means of 100 progeny groups with first and 76 with second lactations. Correlations of second lactation culling rate with dairy character and with rear udder were approximately -.4. Persistency, measured in either first or second lactation, was negatively associated with all type traits.     

Changes in growth kinetics and motility characteristics of Escherichia coli in the presence of sulphoraphane isolated from broccoli seed meal

In this investigation, the purified sulphoraphane from broccoli seed meal was evaluated in a range of 5–400 μg mL⁻¹ against Escherichia coli. The results showed that levels above 200 μg mL⁻¹ can inhibit 100% growth of 10⁶ CFU mL⁻¹ up to 5 h and cause a deformation of sigmoid behaviour in the growth kinetics, and even the bacterial population is reduced. On the other hand, low sulphoraphane levels such as 5–25 μg mL⁻¹ also have effects on the bacterium, such as the decrease in the maximum specific growth rate and the loss of ability to adjust to a growth model when maintained in isothermal conditions. In addition, sulphoraphane has an effect on swimming motility and swarming motility in semi-solid medium. The interaction of natural sulphoraphane–E. coli and the effect in the short periods can draw attention in research on food science and technology.     

Reactions of chickpea to water stress: yield and seed composition

Drought after podding is a common feature of chickpea production in south‐western Australia. We studied the effect of water stress, imposed after podding, on yield and on the accumulation of amino acids and soluble sugars in seeds. Although terminal water stress decreased the total plant dry mass and seed yield by 23% and 30% respectively, it had no effect on the mass of individual pods and seeds which remained on the plant after the imposition of stress treatment. The deleterious effect of water stress on yield was due to increased pod abortion and a decrease in pod formation. Water stress improved the seed's nutritive value in terms of higher accumulation of soluble sugars, amino acids and proteins. © 2001 Society of Chemical Industry     

Characteristics of nucleation and growth events of ultrafine particles measured in Rochester, NY

Number concentrations and size distributions of particles in the size range of 0.010-0.500 microm were measured in Rochester, NY, from December 2001 to December 2002. The relationships between the number concentrations, gaseous pollutants, and meteorological parameters were examined during particle nucleation events. More than 70% of measured total number concentration was associated with ultrafine particles (UFP, 0.011-0.050 microm). Morning nucleation events typically peaking UFP number concentrations at around 08:00 were apparent in winter months with CO increases. These particles appear to be formed following direct emissions from motorvehicles during morning rush hour. There were also often observed increases in this smaller-sized range particles in the late afternoon during the afternoon rush hour, particularly in winter when the mixing heights remain lowerthan in summer. Strong afternoon nucleation events (> 30,000 cm(-3)) peaking at around 13: 00 were more likely to occur in spiring and summer months. During the prominent nucleation events, peaks of SO2 were strongly associated with the number concentrations of UFP, whereas there were no significant correlations between these events and PM2.5 and CO. Increased SO2 concentrations were observed when the wind direction was northwesterly where three SO2 sources were located. It is hypothesized that UFP formed during the events are sulfuric acid and water from the oxidation of SO2. There were also a more limited number of nucleation events followed by particle growth up to approximately 0.1 microm over periods of up to 18 h. The nucleation and growth events tended to be common in spring months especially in April.     

Effect of a calcium peroxide seed coating on the establishment and yield of winter wheat sown by direct drilling in the presence of straw residues

Seed coated with a formulation containing calcium peroxide slightly improved establishment and yield of winter wheat direct-drilled in the presence of straw residues compared with wheat seed coated with a commercial fungicide/pesticide. There was no benefit in the presence of stubble or after burning. Even with the peroxide coating the yield of the crop direct-drilled into chopped straw was 33% less than where the residues had been burnt.     

Direct evidence of atmospheric secondary organic aerosol formation in forest atmosphere through heteromolecular nucleation

Atmospheric aerosols play a central role in climate and atmospheric chemistry. Organic matter frequently composes aerosol major fraction over continental areas. Reactions of natural volatile organic compounds, with atmospheric oxidants, are a key formation pathway of fine particles. The gas and particle atmospheric concentration of organic compounds directly emitted from conifer leaf epicuticular wax and of those formed through the photooxidation of alpha- and beta-pinene were simultaneously collected and measured in a conifer forest by using elaborated sampling and GC/ MS techniques. The saturation concentrations of acidic and carbonyl photooxidation products were estimated, by taking into consideration primary gas- and particle-phase organic species. Primary organic aerosol components represented an important fraction of the atmospheric gas-phase organic content Consequently, saturation concentrations of photooxidation products have been lowered facilitating new particle formation between molecules of photooxidation products and semi-volatile organic compounds. From the measured concentrations of the above-mentioned compounds, saturation concentrations (Csat,i) of alpha- and beta-pinene photooxidation products were calculated for nonideal conditions using a previously developed absorptive model. The results of these calculations indicated that primarily emitted organic species and ambient temperature play a crucial role in secondary organic aerosol formation.     

Isothermal batch crystallization of alpha-lactose: A kinetic model combining mutarotation,nucleation and growth steps

A kinetic model combining first-order differential equations of the three consecutive steps of lactose crystallization, i.e., mutarotation, nucleation and crystal growth rate, was developed. Numerical solutions successfully fitted the variations of crystal mass growth rate as a function of lactose concentration during unseeded isothermal batch crystallization, at different initial lactose concentrations and temperatures. The model allowed the induction phase and the influence of seeding to be simulated by taking into account the dependency of crystal growth rate on total crystal surface area and, consequently, on nucleation rate. The proposed model highlights the large influence of the mutarotation step, even in unseeded crystallization kinetics. The effects of high lactose supersaturations that prevail at industrial scale during whey powder manufacturing and the effects of alkaline pH (9.5) on lactose crystallization kinetic were successfully predicted.     

电子烟抽吸参数、电池功率、雾化剂配比对气溶胶中烟碱释放量的影响研究

为客观评价影响电子烟烟碱释放量的因素,采用电子烟综合测试平台研究电子烟抽吸参数、电池功率、雾化剂配比等条件对电子烟气溶胶中烟碱释放量的影响。结果表明:1）抽吸曲线、抽吸持续时间和抽吸容量是影响电子烟气溶胶烟碱释放量的主要因素,抽吸频率对电子烟气溶胶烟碱释放量影响的程度较小;2）在导油棉正常导油条件下,电子烟烟碱释放量随电子烟电池功率的增大而增加;3）对于雾化剂为丙二醇和丙三醇的电子烟,丙二醇的含量越高电子烟烟碱释放量越高。      

硒、锌对甘蓝型油菜产量和营养品质的影响

采用土培试验,以甘蓝型油菜为供试作物,研究了陕西渭北旱塬低硒、低锌土壤上,硒、锌对甘蓝型油菜产量和营养品质的影响。试验结果表明,硒对油菜生物量和产量没有明显的影响。锌或硒锌配施对油菜生物量和产量有增加趋势;施硒促进油菜籽对钾、硒元素的吸收累积,而在一定程度上抑制了磷、硫、钙和镁元素的吸收。施锌促进油菜对钾、钙、铁、锰、铜、锌、硼的吸收累积,而对氮、硫的吸收有抑制作用。硒锌配合施用有利于促进油菜对硒、锌的吸收累积,而对铁的吸收有一定的抑制作用;施硒对油菜籽含油量、芥酸有增加趋势,对蛋白质、硫甙含量有降低趋势。施锌对油菜籽含油量有增加趋势,对蛋白质、硫甙、芥酸有降低趋势。硒锌配施,油菜含油量、蛋白质、硫甙无变化,芥酸明显下降。     

Chilling effects during seed filling on accumulation of seed reserves and yield of chickpea

Chilling (<15 °C) during the reproductive phase of chickpea leads to abortion of flowers and pods, infertile pods, smaller seeds and reduced seed yields. In the present study, effects of chilling during seed development were evaluated on accumulation of seed reserves and yield parameters in an extra early maturing chickpea genotype ICCV 96 029. Relative to control plants (17/28 °C mean minimum/maximum temperature), those subjected to cold stress (5/13 °C mean minimum/maximum temperature) showed a marked increase in electrolyte leakage, while cellular respiration (assessed as 2,3,5‐triphenyl tetrazolium chloride reduction activity), chlorophyll content, relative leaf water content and rate and duration of seed filling decreased significantly. In cold‐stressed plants, seed number per 100 pods, seed weight per plant, average seed weight and average seed size decreased by 35, 43, 41 and 24% respectively. Seed reserves of starch, protein and fat decreased by 34, 33 and 43% respectively, while total soluble sugars increased twofold. The accumulation of storage proteins such as globulins and albumins was inhibited to a greater extent than that of prolamins and glutelins. Most of the amino acids decreased as a result of stress, while some such as proline and glutamic acid increased significantly. Among the minerals examined, phosphorus content decreased more than calcium and iron contents. Copyright © 2005 Society of Chemical Industry     

Sesquiterpene emissions from pine trees--identifications, emission rates and flux estimates for the contiguous United States

Biogenic volatile organic compound (BVOC) emissions were studied using vegetation enclosure experiments. Particular emphasis was given to sesquiterpene compounds (SQT), although monoterpenes (MT) were also characterized. SQT were detected in emissions from seven (out of eight) pine species that were examined. Thirteen SQT compounds were identified; the most abundant ones were beta-caryophyllene, alpha-bergamotene, beta-farnesene, and alpha-farnesene, with emission rates increasing exponentially with temperature. Regression analysis yielded exponential dependencies of both MT and SQT emissions on temperature of the form E = E0 x exp(beta(T - T0)). This resulted in SQT basal emission rates (E0 defined at T0 = 30 degrees C) ranging between <4 and 620 ng (carbon) gdw(-1) h(-1) (gdw = gram dry weight). The average value of the exponential temperature response factor beta for SQT emissions, taken from all experiments, was 0.17 degree C(-1), whereas the value for monoterpenes was 0.11 degrees C(-1). The average, total SQT emissions from pines were estimated to be 9, 16, and 29% of the MT emissions at 20, 30, and 40 degrees C respectively. The emission factors and beta-factors determined from these measurements were used to estimate pine tree MT and SQT emission distributions for the contiguous United States using MEGAN (model of emissions of gases and aerosols from nature, Guenther et al., 2006). SQT fluxes reaching 10-40 mg m(-2) for the month of July were estimated for extensive areas of most western and southern U.S. states.     

Effect of seed moisture content on the grinding kinetics,yield and quality of soybean oil

Grinding kinetics of soybeans at different moisture content (6%, 8% and 12%) were investigated. The hardness of soybean particles increased and showed brittle characters as the moisture content decreased. Three theoretical models for grinding, such as the Rittinger, Kick, and Bond model, were applied to characterize the grinding process of soybeans. The lower moisture content showed less grinding constants including Bond’s work index. Sigmoid model was successfully applied to describe the changes in particle size of soybeans at different moisture contents during grinding (r² > 0.96). The TBARS (thiobarbituric acid reactive substances) at different size of soybean flours were measured at 25 °C and 50 °C for 20 days and the yield of oil composition at different size of soybean flours were measured. As the particle sizes decreased, the TBARS values increased during storage, while the oil yield from soybean flours increased.