Promotive effect of se on the growth and antioxidation of a blue-green algaSpirulina maxima

Cultures of a blue-green algaSpirulina maxima (Setch. et Gard.) Geitler with various concentrations of Se in Zarrouk's medium showed that not higher than 40 mg/L Se could promote its growth. The present experiments showed thatS. maxima grown under normal conditions, has an oxidant stress defence system for hydrogen peroxide (H₂O₂) removal, which is the Halliwell-Asada pathway. When 4 to 20 mg/L Se was added to the algal medium, this pathway was replaced by a so-called Sestressed pathway containing GSH peroxidase (GSH-POD). As a result of the occurrence of both higher activity of GSH-POD and lower levels of hydroxyl radical (OH·), the Se-stressed pathway scavenged H₂O₂ so effectively that the growth ofS. maxima was promoted by 4 to 20 mg/L Se. While GSH-POD activity of the alga disappeared at 40 mg/L Se, the recovery of ascorbate peroxidase was observed. The lower levels of ascorbic acid and GSH made the Halliwell-Asada pathway for scavenging H₂O₂ less effective, while the highest activity of catalase might be responsible in part for the H₂O₂ removal, causing the level of OH· inS. maxima grown at 40 mg/L Se to be much higher than the OH· level in this alga grown at 4 to 20 mg/L Se, but lower than that in the control. The OH· level changes caused the growth ofS. maxima cultured at 40 mg/L Se to increase slightly to close to that of the control.     

On the Exchange of NO3 Radicals with Aqueous Solutions: Solubility and Sticking Coefficient

The exchange of NO₃ radicals with the aqueous-phase was investigated at room temperature (293 K) in a series of wetted denuders. From these experiments, the uptake coefficient of NO₃ was determined on 0.1 M NaCl solutions and was found to be (NO₃) 2 × 10^-3 in good agreement with recent studies. The Henry coefficient of NO₃ was estimated to be K_H(NO₃) = 1.8 M · atm^-1, with a (2) uncertainty of ±3 M · atm^-1. From the upper limit for the Henry coefficient (K_H = 5 M · atm^-1) and available thermodynamic data, the redox potential of dissolved NO₃/NO ₃ ^– is estimated to be in the range of 2.3 to 2.5 V. This range is at the lower boundary of earlier estimates. The results are discussed in the light of a recent publication. Based on our data and a model of the transport and chemistry in the liquid film, an upper limit is derived for the product of the Henry coefficient K_H and the rate coefficient k ₁₀ of the potential reaction NO₃ + H₂O HNO₃ + OH. For K_H = 0.6 M · atm^-1, we find k ₁₀ < 0.05 s^-1 · atm^-1, i.e., about 100 times smaller than what was suggested by Rudich and co-workers. Because of its small solubility, heterogeneous removal of NO₃ is only important under conditions where the dissolved NO₃ is removed quickly from equilibrium, for example by reactions with Cl^– or HSO ₃ ^– ions in the liquid-phase. Otherwise, heterogenous removal should mainly proceed via N₂O₅.     

Free Radicals and Fast Photochemistry during BERLIOZ

The free radicals OH, HO₂, RO₂, and NO₃ are known to be the driving force for most chemical processes in the atmosphere. Since the low concentration of the above radicals makes measurements particularly difficult, only relatively few direct measurements of free radical concentrations have been reported to date.We present a comprehensive set of simultaneous radical measurements performed by Laser Induced Fluorescence (LIF), Matrix Isolation –Electron spin Resonance (MI-ESR), Peroxy Radical Chemical Amplification (PERCA), and Differential Optical Absorption Spectroscopy (DOAS) during the BERLIner OZonexperiment (BERLIOZ) during July and August of 1998 near Berlin, Germany. Most of the above radical species were measured by more than one technique and an intercomparison gave good agreement. This data set offered the possibility to study and quantify the role of each radical at a rural, semi-polluted site in the continental boundary layer and to investigate interconnections and dependencies among these free radicals.In general (box) modelled diurnal profiles of the different radicals reproduced the measurements quite well, however measured absolute levels are frequently lower than model predictions. These discrepancies point to disturbing deficiencies in our understanding of the chemical system in urban air masses.In addition considerable night-time peroxy radical production related to VOC reactions with NO₃ and O₃ could be quantified.     

Mechanisms and products of the reactions of NO3 with cycloalkenes

The NO₃ radical initiated oxidation of cyclopentene, cyclohexene and 1-methyl-cyclohexene has been studied. The products formed in an N₂O₅-NO₂-N₂-O₂-cycloalkene-static reactor system, at 0.1 MPa and 296 K, were investigated using long path FTIR. The principal products were aldehydes formed via a ring opening process. The reactions also resulted in significant yields of three types of ring retaining nitrooxy-substituted compounds. The average yields of alkyl nitrates from, e.g., reactions with cycloalkene were 25.1% 2-oxo-cyclohexyl nitrate, 22.8% 2-hydroxy-cyclohexyl nitrate and 4.0% 1,2-cyclohexyl dinitrate. The mechanisms involved resembles those proposed for acyclic alkenes. In absence of NO, -oxo and -hydroxy-cycloalkyl nitrates are formed via self reactions of -nitrooxy substituted cycloalkyl peroxy radicals. Estimated branching ratios for the reactants leading to ring retaining products in the presence and in the absence of NO are given and the possible relevance of these reactions for cycloalkenes under tropospheric conditions is discussed.     

High mercury levels in hair samples from residents of Taiji, a Japanese whaling town

We investigated the mercury concentrations in red meat from pilot whales consumed by some residents of the Japanese whaling town, Taiji, and in hair samples from 50 residents for their maker of mercury burden. The methyl mercury (M-Hg) level in the red meat was 5.9 μg/wet g, markedly higher than the US FDA action level and Cordex Alimentarius guideline level for predatory fish (1.0 μg/wet g). The average level of total mercury (T-Hg) in the hair from residents who ate whale meat more than once a month was 24.6 μg/g, whereas the average from the residents who did not consume any whale meat was 4.3 μg/g. The T-Hg concentrations in the hair from three donors exceeded 50 μg/g, the level for NOAEL set by WHO. The T-Hg level found in the Taiji whale meat consumers was markedly higher than that observed in the Japanese population overall (about 2 μg/g).     

两种由群的元素性质所确定的群的根性

讨论群的元素性质与群的根性之间的关系．考虑群的元素性质汐满足条件（1）：如果x是p-的p-元素,且N G,那么xN是G／N的p-元素;满足条件（4）：设N G,如果x∈N是G的p-元素,那么x也是N的p-元素,则群类P1={G}G的每个同态像没有非平凡的p-元素}是p1-根群类．如果p满足条件（1）和条件（2）,x∈N是N的p-元素,且N G,那么x也是G的p-元素,则群类P2={G｜G的每个非平凡的同态像有一个非平凡的次正规p-子群}是p-根群类．如果性质p-满足条件（1）,（2）和（4）,那么P,P2均为根群类且P=P2．     

Hydroxyl and Peroxy Radical Chemistry in a Rural Area of Central Pennsylvania: Observations and Model Comparisons

Atmospheric hydroxyl (OH), hydroperoxy (HO₂), total peroxy (HO₂ and organic peroxy radicals, RO₂) mixing ratios and OH reactivity (first order OH loss rate) were measured at a rural site in central Pennsylvania during May and June 2002. OH and HO₂ mixing ratios were measured with laser induced fluorescence (LIF); HO₂ + RO₂ mixing ratios were measured with chemical ionization mass spectrometry (CIMS). The daytime maximum mixing ratios were up to 0.6 parts per trillion by volume (pptv) for OH, 30 pptv for HO₂, and 45 pptv for HO₂ + RO₂. A parameterized RACM (Regional Atmospheric Chemistry Mechanism) box model was used to predict steady state OH, HO₂ and HO₂ + RO₂ concentrations by constraining the model to the measured OH reactivity and previously measured volatile organic compound (VOC) distributions. The averaged model calculations are generally in good agreement with the observations. For OH, the model matched the observations for day and night, with an average observed-to-modeled ratio of 0.80. In previous studies such as PROPHET98, nighttime NO was near 0 pptv and observed nighttime OH was significantly larger than modeled OH. In this study, nighttime observed and modeled OH agree to within measurement and model uncertainties because the main source of the nighttime OH was the reaction HO₂ + NO → OH + NO₂, with the NO being continually emitted from the surrounding fertilized corn field. The observed-to-modeled ratio for HO₂ is 1.0 on average, although daytime HO₂ is underpredicted by a factor of 1.2 and nighttime HO₂ is over-predicted by a factor of ∼2. The average measured and modeled HO₂ + RO₂ agree well during daytime, but the modeled value is about twice the measured value during nighttime. While measured HO₂ + RO₂ values agree with modeled values for NO mixing ratios less than a few parts per billion by volume (ppbv), it increases substantially above the expected value for NO greater than a few ppbv. This observation of the higher-than-expected HO₂ + RO₂ with the CIMS technique confirms the observed increase of HO₂ above expected values at higher NO mixing ratios in HO₂ measurements with the LIF technique. The maximum instantaneous O₃ production rate calculated from HO₂ and RO₂ reactions with NO was as high as 10–15 ppb h⁻¹ at midday; the total daily O₃ production varied from 13 to 113 ppbv d⁻¹ and was 48 ppbv d⁻¹ on average during this campaign.     

Peroxy Radical Concentrations Measured at a Forest Canopy in Nikko,Japan, in Summer 2002

Concentrations of peroxy radicals were measured by a chemical amplification technique at a remote forested site as part of the Program for Research on Oxidants in a Forested Region in Nikko (PROFRN). During the measurement period of 22–27 July 2002, the mixing ratios of peroxy radicals averaged for 3 min at midday ranged from 109 to 134 pptv at a height approximately 5 m above the forest canopy. Significant diurnal variation in concentrations of peroxy radicals was observed, with the maximum usually occurring around noon. Most of the variation was driven by changes in the intensity of solar radiation. However, it was found that the peroxy radical concentration reached its peak about 3-h later than that of solar radiation on 24 and 26 July. The origins of this delay are discussed based on an analysis of the total radical budget in that period. A transport of polluted air masses to the site was one of possible causes for the inconsistency. In addition, the measured peroxy radical concentrations were compared with those derived from the deviations of NO-NO₂-O₃ photo-stationary state (PSSD) for clear days. The estimated half-hour-average concentrations of peroxy radical were in agreement with the PERCA measured in the morning and late afternoon. However the two techniques differed by as much as a factor of two during the time of near midday.     

Spectra of the ammonium radical: the schüler bands

The main bands of the Schüler system of ND₄ and NH₄ have been observed at high resolution. On the basis of these spectra, Watson, in a separate paper, has analysed the ND₄ main band showing that it represents a²F₂ → ² A₁ transition of a tetrahedral molecule. The observed wavenumber data for both ND₄ and NH₄ are presented; the latter have not yet been analysed. Isotopic bands for¹⁵ND₄,¹⁴ND₃H,¹⁴ND₂H₂,¹⁴NDH₃ have also been obtained and as previously pointed out confirm the assumed carrier of the spectrum. The much weaker bands accompanying the main Schüler band on the short and long wavelength sides are photographed at medium resolution. The interpretation of these bands in terms of the vibrational levels of upper and lower states is briefly discussed.     

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.