An Atmospheric Chemistry Interpretation of Mass Scans Obtained from a Proton Transfer Mass Spectrometer Flown over the Tropical Rainforest of Surinam

Data on a variety of organic gases are presented, obtained with a protontransfer mass spectrometer (PTR-MS) operated during the March 1998 LBA/CLAIREairborne measurement campaign, between 60 and 12500 m over the rainforest inSurinam (2° N–5° N, 54° W–57° W). The instrumentcan detect molecules with a proton affinity greater than water, includingalkenes, dialkenes, carbonyls, alcohols, and nitriles. Many such molecules areemitted from the rainforest (e.g., isoprene) or formed from the oxidation ofprimary emissions (e.g., methylvinylketone (MVK) and methacrolein (MACR)).From a comparison with modelled data; the variation with altitude; previouslyreported biogenic emissions and the time and location of the measurement,possible and probable identities for the significant masses encountered in therange 33–140 amu have been deduced.The main observed protonated masses, postulated identities and observedaverage boundary layer mixing ratios over the rainforest were: 33 methanol(1.1 nmol/mol); 42 acetonitrile (190 pmol/mol); 43 multiple possibilities (5.9nmol/mol), 45 acetaldehyde (1.7 nmol/mol), 47 formic acid (not quantified);59 acetone (2.9 nmol/mol), 61 acetic acid (not quantified), 63 dimethylsulphide (DMS) (289 pmol/mol), 69 isoprene (1.7 nmol/mol), 71 MVK + MACR (1.3nmol/mol), 73 methyl ethyl ketone (1.8 nmol/mol), 75 hydroxyacetone (606pmol/mol), 83 C₅ isoprene hydroxy carbonylsC₅H₈O₂, methyl furan, and cis 3-hexen-1-ol(732 pmol/mol), 87 C₅ carbonyls and methacrylic acid, 95 possibly2-vinyl furan (656 pmol/mol), 97 unknown (305 pmol/mol), 99 cis hexenal (512pmol/mol) and 101 isoprene C₅ hydroperoxides (575 pmol/mol). Somespecies agreed well with those derived from an isoprene only photochemicalmodel (e.g., mass 71 MVK + MACR) while others did not and were observed athigher than previously reported mixing ratios (e.g., mass 59 acetone, mass 63DMS). Monoterpenes were not detected above the detection limit of 300pmol/mol. Several species postulated are potentially important sources ofHO_x in the free troposphere, e.g., methanol, acetone, methyl ethylketone, methyl vinyl ketone and methacrolein.     

Alkyl nitrates and bifunctional nitrates of atmospheric interest: Henry's law constants and their temperature dependencies

Henry's law coefficients of 15 alkyl nitrates, keto-, hydroxy-, and dinitrates of atmospheric interest have been measured, mostly over the temperature range 1–25°C. The compounds are stable in aqueous solution. Where literature data were available, Henry's law coefficients are in very good agreement. It is concluded that dissolution in cloud and rain water is not an important loss process for alkyl mononitrates in the atmosphere. The residence times of the more soluble bifunctional organic nitrates, however, are significantly affected or even controlled by washout and rainout. Gas chromatographic analysis of bifunctional nitrates in preconcentrated atmospheric samples may be adversely affected by the adsorptive properties of these compounds.     

Comparison of Chlorophyll a Concentrations Obtained with 90% Acetone and N,N-dimethylformamide Extraction in Coastal Seawater

Determinations of Chlorophyll a (Chl a) in eutrophic coastal marine waters were compared using N, N-dimethylformamide (DMF) and 90% acetone techniques. Measured Chl a concentrations ranged from 0.89 to 10.65 μg l₋₁ for 90% acetone extracts and from 0.97 to 12.92 μg l⁻¹ for DMF extracts, respectively, for 24 surface water samples from the Harima-nada, Seto Inland Sea, Japan. Chl a concentrations using DMF as a solvent were consistently higher than those found using 90% acetone (p < 0.001, n= 24). Chl a is thus likely to be underestimated (by 13%) when 90% acetone is used for eutrophic waters. This revised version was published online in July 2006 with corrections to the Cover Date.     

CS2/NMP extraction of immature source rock concentrates

Eleven Chinese immature source rock concentrates from the immature oil formations in four different depressions were extracted ultrasonically with a mixture of CS₂ and N-methyl-2-pyrrolidinone (CS₂/NMP) at room temperature. The samples were also extracted with CHCl₃ and a mixture of methanol/acetone/chloroform (MAC) for comparison. The solvent system CS₂/NMP is very efficient for the extraction of immature source rock concentrates, giving much higher extraction yields than CHCl₃ or MAC. The composition of the extracts using different solvent mixtures is also different. Model compound tests indicate that no chemical reactions have taken place between the NMP and the substrates in the extraction. These results suggest that there are abundant non-covalent bond interactions in the organic matter of the immature source rock concentrates. The fact that CS₂/NMP mixed solvent extracts more than MAC and CHCl₃ is not only because it can dissolve higher molecular weight fractions, but also because it has stronger ability to disrupt the complex interactions existing between the soluble and insoluble fractions. Biomarker distributions in the saturated hydrocarbon fractions are different for different solvent systems, suggesting that care should be taken when comparing the biomarker parameters in source rocks when using different solvents for extraction.     

铼-锇同位素定年法中丙酮萃取铼的系统研究

文章较为系统地研究了铼-锇定年法中丙酮萃取铼的实验条件,对萃取介质的碱度和萃取剂的用量进行了优化,并对振荡萃取时间以及碱洗进行了选择。优化后的实验条件对铼有较高的回收率,对其他杂质元素也有较高的分离系数,不仅简化了实验流程,而且节约了化学试剂。     

Gas-Phase OH Oxidation of Monoterpenes: Gaseous and Particulate Products

Smog chamber experiments have beenconducted in which cyclic monoterpenes were oxidisedin the gas phase by OH. The evolved secondary organicaerosol (SOA) was analysed by LC-MSⁿ and thegas-phase products were analysed by FT-IR. Theconcentrations of the identified compoundscorresponded to carbon mass balances in the range of40%–90%. The identified compounds in the particularphase corresponded to 0.5%–4.2% of the reactedcarbon. The most abundant compounds in SOA fromterpenes with an endocyclic C=C double bond wereC₁₀-keto-aldehydes, C₁₀-keto-carboxylicacids, C₁₀-hydroxy-keto-carboxylic acids, andC₁₀-hydroxy-keto-aldehydes (pinonaldehyde,pinonic acid, hydroxy-pinonic acid isomers, andhydroxy-pinonaldehyde isomers from -pinene;3-caronaldehyde, 3-caronic acid, hydroxy-3-caronicacid isomers, and hydroxy-3-caronaldehyde isomers from3-carene). The most abundant compounds in SOA fromterpenes with an exocyclic C=C double bond wereC₉-ketones, C₉-dicarboxylic acids, andC₁₀-hydroxy-keto-carboxylic acids (nopinone,pinic acid, and hydroxy-pinonic acid isomers from-pinene; sabinaketone, sabinic acid andhydroxy-sabinonic acid isomers from sabinene).Decarboxylated analogues of most of the compounds werepresent in SOA in minor concentrations, such asC₉-keto-carboxylic acids (norpinonic acid,nor-3-caronic acid) and C₈-dicarboxylic acids(norpinic acid, nor-3-caric acid, norsabinic acid). InSOA from limonene, which contains an endocyclic aswell as an exocyclic C=C double bond, the mostabundant compounds were a C₁₀-keto-aldehyde andits oxo-derivative (limononaldehyde and keto-limononaldehyde) together with hydroxy-derivatives of aC₁₀-keto-carboxylic acid (isomers ofhydroxy-limononic acid). Also aC₁₀-keto-carboxylic acid (limononic acid) waspresent together with minor concentrations of aC₉-dicarboxylic acids (limonic acid), itsoxo-derivative (keto-limonic acid), and itsdecarboxylated analogue (norlimonic acid). Mechanisticpathways for the formation of these products, some ofwhich are identified here for the first time, areproposed.     

浮游植物叶绿素a含量不同方法测定比较——以白洋淀区域水体为例

实验使用国际上较通用的热乙醇萃取分光光度法、国内常用的丙酮萃取分光光度法、BBE藻类分类测定仪及YSI多参数测定仪测定浮游植物的叶绿素a,并将这4种方法的测定结果进行了比较。结果表明丙酮法的测定结果相对较高;BBE藻类分类仪检测叶绿素a较接近于乙醇法的叶绿素a的测定结果,线性关系和回归系数也最好,丙酮法测定的结果次之,YSI现场多参数检测结果与乙醇法叶绿素a的测定结果差别较大。实验得出,BBE藻类分类仪检测结果可进行部分采用,而YSI现场多参数检测结果可作为实验的参考值,而且离心的步骤省略对实验结果影响较大。