Organic aerosol formation from photochemical oxidation of diesel exhaust in a smog chamber

Diluted exhaust from a diesel engine was photo-oxidized in a smog chamber to investigate secondary organic aerosol (SOA) production. Photochemical aging rapidly produces significant SOA, almost doubling the organic aerosol contribution of primary emissions after several hours of processing at atmospherically relevant hydroxyl radical concentrations. Less than 10% of the SOA mass can be explained using a SOA model and the measured oxidation of known precursors such as light aromatics. However, the ultimate yield of SOA is uncertain because it is sensitive to treatment of particle and vapor losses to the chamber walls. Mass spectra from an aerosol mass spectrometer (AMS) reveal that the organic aerosol becomes progressively more oxidized throughout the experiments, consistent with sustained, multi-generational production. The data provide strong evidence that the oxidation of a wide array of precursors that are currently not accounted for in existing models contributes to ambient SOA formation.     

Aqueous photochemical reaction kinetics and transformations of fluoxetine

Fluoxetine (FLX) was shown to be photoreactive in sunlit surface waters. FLX degraded in deionized water when exposed to simulated sunlight with a half-life of 55.2+/-3.6 h(-1). Photodegradation products were identified using high performance liquid chromatography-UV (HPLC-UV) and liquid chromatography tandem mass spectrometry (LC-MS-MS) using electrospray (ES) ionization. Defluorination of the trifluoromethyl group in FLX and in fluometuron and flutalanil,two other compounds containing this functional group, is suggested to be a common direct photolysis pathway for trifluoromethylated compounds. Products resulting from O-dealkylation of FLX were also observed. The rate of degradation was faster in synthetic field water where .OH was the likely dominant oxidant in the system. The bimolecular rate constant for the reaction between FLX and .OH was measured as (8.4+/-0.5) x 10(9) and (9.6 +/-0.8) x 10(9) M(-1) s(-1) using two different methods of competition kinetics. Indirect photodegradation reactions could lead to the production of hydroxylated and O-dealkylated compounds. Although direct photolysis could potentially limitthe persistence of FLX in surface waters, its degradation by indirect photolysis would proceed faster. Thus, this latter process could be important in the elimination of FLX in surface waters.     

Furan formation from vitamin C in a starch-based model system: Influence of the reaction conditions

The generation of furan from vitamin C during thermal treatment of a starch-based model system, which simulated baby food, was studied. Results indicated that the amount of sample heated in the vial influenced the furan generation from ascorbic acid. Increasing the amount of heated sample from 5% to approximately 98% of the total vial volume, drastically reduced furan formation from 70 ppb to 16 ppb. Changes in ascorbic acid concentrations from 0.1 to 4.5 mg/g did not influence furan concentration nor did different ascorbic/dehydroascorbic acid molar ratios. Interestingly, waxy corn starch itself considerably enhanced furan generation from ascorbic acid. Under the same conditions, 13.2 ppb of furan was generated in starch-based samples, while in ascorbic acid buffered solutions only 0.4 ppb of furan was formed. Application of other matrices, in particular agar and hydrolysed starch, resulted in similar furan concentrations as for native starch, while in polyol solutions furan concentrations were comparable to those obtained for the buffered ascorbic acid solutions.     

The formation of IQ type mutagens from Maillard reaction in ethanolic solution

The present study mimics cooking meats in alcohol or distilled spirit marinades by using a 0.1 M creatinine/0.05 M sugars/0.1 M threonine ethanolic model solution, in an attempt to investigate the formation of the heterocyclic amines IQ and IQx, via Maillard reaction. The results showed that ethanol accelerated the formation of IQ and IQx, in a dose-dependent manner. In an aqueous model solution of 0.1 M creatinine/0.05 M glucose/0.1 M threonine after 8 h heating at 150 °C, the contents of IQ and IQx are 16.5 ± 2.2 and 26.2 ± 4.2 mg/kg, respectively. However, at a similar Maillard browning level in the equivalent 50% ethanolic model solution after heating at the same temperature for only 4 h, the contents of IQ and IQx significantly increase to 46.0 ± 5.5 and 69.2 ± 3.4 mg/kg, respectively.     

甘油与氯化钠模型热反应中生成3-氯-1,2-丙二醇的研究

以甘油、氯化钠、水为原料建立热反应模型,结合气相色谱-质谱法(gas chromatography-mass spectrometry,GC-MS)分析,对其生成的3-氯-1,2-丙二醇(3-MCPD)进行了研究.通过正交实验,考察了反应时间、温度和各原料用量对3-MCPD生成量的影响,同时研究了在热反应模型中分别加入不同种类单糖和氨基酸后3-MCPD生成量的变化规律,并对其反应机理进行了探讨.结果表明,反应时间2h、反应温度140℃、甘油用量0.05g(占原料总量0.31％)、NaCl用量1.0g(6.23％)、水用量15g(93.46％),3-MCPD生成量最少;葡萄糖、果糖、木糖、甘露糖、半乳糖、缬氨酸、精氨酸、赖氨酸、丝氨酸、亮氨酸、苯丙氨酸、苏氨酸、组氨酸使3-MCPD的生成量减少;谷氨酸、蛋氨酸、丙氨酸、天冬氨酸、甘氨酸使3-MCPD的生成量增加;半胱氨酸、酪氨酸、脯氨酸、色氨酸对3-MCPD的生成无明显作用.     

生化反应中一类多分子反应的非线性分析

研究了生化反应中一类多分子反应方程:x=1-αx-xy,y=β(xy-y)(α>0, β>0,q≥2).主要讨论了平衡点的稳定性态,系统无环的充分条件以及极限环的存在性.     

Determination of dl-alpha-tocopherol acetate and dl-alpha-tocopherol in foods by HPLC using post-column photochemical reaction

A reliable analytical method for the simultaneous determination of dl-alpha-tocopherol acetate and dl-alpha-tocopherol in foods was established by HPLC using post-column photochemical reaction with UV and fluorescence detection. For low-fat food such as fruit juice and vegetable sauce, the tocopherols were extracted with methanol containing 0.1% ascorbic acid and the extract solution was injected into the HPLC. For fatty foods such as butter and margarine, the tocopherols were extracted with a mixed solvent of acetonitrile-2-propanol (9:1) containing ascorbic acid. The extract was cleaned up using a Sep Pak plus C18 cartridge and the eluent from the cartridge was injected into the HPLC. The peaks corresponding to tocopherols on the chromatogram were confirmed by comparing their UV spectra with those of the standard mixture at lamp-on and lamp-off of the photochemical reactor. The recoveries of tocopherols from low-fat foods (orange juice and barbecue sauce) fortified at levels of 10 and 100 microg/kg each were 88.3 to 105.8% (RSD 0.5 to 6.0%) and those from the fatty foods (peanut butter and margarine) fortified at 100 microg/kg each were 57.1 to 88.3% (RSD 3.0 to 6.4%). The determination limits corresponded to 10 microg/kg of the tocopherols in the low-fat foods and 20 microg/kg in the fatty foods.     

Key meat flavour compounds formation mechanism in a glutathione-xylose Maillard reaction

The formation mechanism of meat flavours formed from a glutathione-xylose Maillard reaction was studied using a group of model reactions with [¹³C₅] xylose/xylose (1:1), heated at 132 °C for 90 min. Volatiles, especially the aroma-active compounds, and non-volatiles were analysed respectively with GC-O-MS and LC-TOF-MS. Analysis of the mass spectra showed that furfural, 2-furfurylthiol and thiophene were ¹³C₅-labelled and hence stem from xylose, whereas 2-methyl-3-furanthiol, 2-methyl-thiophene and 2-pentyl-thiophene, which showed similar formation patterns with only unlabelled compounds, may be from thiamine and/or cysteine carbons. In the process of Maillard reactions, GSH can be capable of cleaving in the position of glutamyl and cysteinyl, and then form 5-oxoproline or pyroglutamic acid (PCA), cysteine, and Cys-Gly dipeptide, which can form cyclic (Cys-Gly).     

反应温度和时间对抗坏血酸/精氨酸Maillard反应体系中挥发性化合物形成的影响

采用顶空固相微萃取-气相色谱-质谱联用技术对抗坏血酸/精氨酸反应体系在不同反应温度和时间下的产物进行鉴定,共鉴定出包括吡嗪、醛、呋喃、醇和吲哚在内的24种化合物,其中14种吡嗪化合物为主要香味化合物。考察了反应温度和时间对产物特别是对吡嗪化合物的影响。结果表明,随着反应温度的升高和反应时间的延长,吡嗪类化合物的总量均增加;其中,随反应温度的升高,相对其他吡嗪化合物2-乙基-6-甲基吡嗪、3-乙基-2,5-二甲基吡嗪的量明显增加;随反应时间的延长,2-乙基-6-甲基吡嗪的量明显增加。     

Kinetic mechanism for predicting secondary organic aerosol formation from the reaction of d-limonene with ozone

A semi-explicit mechanism of d-limonene was developed and tested against experimental results obtained from large outdoor Teflon film chambers at the University of North Carolina (UNC) smog chamber facility. The model couples gas-phase reactions with partitioning processes and possible particle-phase reactions. The model not only tracks the gas-phase ozonolysis reaction of d-limonene, but also provides a reasonable prediction of the secondary aerosol mass production under different conditions. Limononaldehyde was the major identified product, followed by limona-ketone, referred to here as keto-limonene, keto-limononaldehyde, limononic acid, and keto-limononic acid. Identified particle-phase products accounted for about 60% of the observed particle mass in the initial stages of the reaction. Model sensitivity was tested and discussed with respect to effects of temperature, humidity, water uptake, and reactant concentrations.     

Deposition versus photochemical removal of PBDEs from Lake Superior air

Analysis of a sediment core collected from Siskiwit Lake, located on a remote island in Lake Superior, provides evidence that polybrominated diphenyl ethers (PBDEs) are removed effectively from the atmosphere via deposition processes during long-range transport. A mass balance model based on photochemical rate constants and data from atmospheric samples was created to understand the relative importance of various photochemical and deposition processes in removing PBDEs from the atmosphere. Photolysis rate constants were derived from UV absorption spectra of 25 PBDEs recorded in isooctane over the range of 280-350 nm at 298 K. Photolysis decays measured for BDE-3 and -7 in the gas phase were substantial compared to a well-defined chemical actinometer, indicating that their photolysis quantum yields are significant. Dibenzofuran production was observed when PBDE congeners containing ortho-bromines were photolyzed in helium. From estimates of removal rates of PBDEs from the lower troposphere, we find that wet and dry deposition accountfor >95% of the removal of BDE-209, while photolysis accounts for -90% of the removal of gas-phase congeners such as BDE-47. These results help explain the deposition patterns of PBDEs found in lake and river sediments and have important implications concerning the inclusion of photolysis as a fate process in multimedia models.     

Bio-guided fractionation of the antimutagenic activity of methanolic extract from the fruit of Randia echinocarpa (Sessé et Mociño) against 1-nitropyrene

Randia echinocarpa is a native plant from Mexico that produces an edible fruit with several ethnopharmacological uses (e.g. cancer, kidney ailments, and diabetes). Extracts of this fruit have shown antimutagenic activity. In this report, a methanolic extract of R. echinocarpa and a bio-guided chromatographic strategy were used to obtain an hexanic fraction (HF) with strong antimutagenic activity (microsuspension assay with Salmonella typhimurium YG1024) using 1-nitropyrene as mutagen (1-NP, 50 and 100 ng/tube). The HF (500 ng/tube) showed the highest inhibition percentage of mutagenic activity (PI) (75%, 1-NP 50 ng/tube; 84%, 1-NP 100 ng/tube). HF chromatography with silica produced HF₁ which was further separated to produce the fractions with the highest antimutagenic activities (HF_1–1 and HF_1–2, PI ≥ 60%). These fractions were chemically characterized by chromatography and gas chromatography–mass spectrometry; among the main components of HF, HF_1–1 and HF_1–2 were registered linoleic acid, palmitic acid and β-sitosterol, which could be responsible for the antimutagenic activity of R. echinocarpa fruit. The samples evaluated were neither toxic nor mutagenic. Randia echinocarpa is an underutilized plant and its fruit has been used traditionally as food/medicine; fruit consumption could provide human health benefits and it has potential to be exploited under conditions of ecological sustainability.     

Atmospheric transport and outflow of polycyclic aromatic hydrocarbons from China

A potential receptor influence function (PRIF) model, based on air mass forward trajectory calculations, was applied to simulate the atmospheric transport and outflow of polycyclic aromatic hydrocarbons (PAHs) emitted from China. With a 10 day atmospheric transport time, most neighboring countries and regions, as well as remote regions, were influenced by PAH emissions from China. Of the total annual PAH emission of 114 Gg, 92.7% remained within the boundary of mainland China. The geographic distribution of PRIFs within China was similar to the geographic distribution of the source regions, with high values in the North China Plain, Sichuan Basin, Shanxi, and Guizhou province. The Tarim basin and Sichuan basin had unfavorable meteorological conditions for PAH outflow. Of the PAH outflow from China (8092 tons or 7.1% of the total annual PAH emission), approximately 69.9% (5655 tons) reached no further than the offshore environment of mainland China and the South China Sea. Approximate 227, 71, 746, and 131 tons PAHs reached North Korea, South Korea, Russia-Mongolia region, and Japan, respectively, 2-4 days after the emission. Only 1.4 tons PAHs reached North America after more than 9 days. Interannual variation in the eastward PAH outflow was positively correlated to cold episodes of El Ni?o/Southern Oscillation. However, trans-Pacific atmospheric transport of PAHs from China was correlated to Pacific North America index (PNA) which is associated with the strength and position of westerly winds.