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Fluorescence detection of organic molecules in the Jovian atmosphere.

A search for fluorescent emission due to the presence of possible organic molecules in the Jovian atmosphere is described. We first consider natural Jovian fluorescent emission excited by precipitating auroral particles. Due to our lack of knowledge of the Jovian precipitation particle energies and fluxes we next consider fluorescent emission excited by a laser system aboard a Jupiter spacecraft. Laser-induced fluorescence is routinely used to monitor trace constituents and pollutants in the terrestrial atmosphere. Several spacecraft laser systems are currently under development. Our calculations indicate that laser-induced fluorescent detection is approximately two orders of magnitude more sensitive than rocket ultraviolet measurements of possible Jovian absorption features at 2600 A that have been attributed to the presence of adenine or benzene.

Atmosphere↗

Organic synthesis from reducing models of the atmosphere of the primitive earth with UV light and electric discharges.

The purpose of this paper is to compare the role of UV light and of electric discharges, the two most important sources of energy on the primitive earth, in the synthesis of organic compounds out of a reducing model of that atmosphere. Since Miller's experiments in 1953, most of the experimental simulations have been performed with electric discharges, and it has been assumed that UV radiations would give similar results. In order to check this assumption we have performed both experimental simulations in our laboratory. Experimental results indicate that this assumption was wrong in a large extent. Our four main conclusions are: 1. Unlike electric discharges, UV light is not an efficient source for producing unsaturated carbon chains. 2. UV light is efficient for producing nitriles in CH4--NH3 mixtures when the mole fraction of NH3 is very low while electric discharges need a higher mole fraction of NH3. 3. UV light is not able to produce nitriles from CH4--N2 mixtures while electric discharges produce important quantities of diversified nitriles from these mixtures. 4. UV light is not very efficient for producing aldehydes from CH4--H2O model atmosphere, electric discharges seem to be able to produce them more efficiently.

Atmosphere↗

The atmospheric environment--an introduction.

The atmosphere is part of the environment with which the human organism is permanently confronted. Epidemiological research investigates the occurrence of effects on morbidity and mortality due to heat, cold, air pollution and changes in the weather. Concentrating on aspects of the environment relevant for medical questions, three major complexes of effects can be discriminated: the complex conditions of heat exchange, the direct biological effects of solar radiation, and air pollution. Biometeorological knowledge can serve to assess the atmospheric environment, and can also be of help in the field of preventive planning, to conserve and develop the climate as a natural resource with regard to man's health, well-being and performance.

Atmosphere↗

Could life have arisen in the primitive atmosphere?

A recently proposed model for the origin of prebiotic progenitors of life in particles suspended in a primitive, specially organized atmosphere is considered critically. It is concluded that the physical and chemical framework of the new hypothesis conflicts with the conditions necessary for the evolution of the progenitors of life in the atmosphere of the early Earth. Therefore this model seems not to be a reasonable alternative to the Oparin thesis.

Atmosphere↗

A multiresidue method using ion-trap gas chromatography-tandem mass spectrometry with or without derivatisation with pentafluorobenzylbromide for the analysis of pesticides in the atmosphere.

A multiresidue method using gas chromatography coupled to ion-trap tandem mass spectrometry (MS/MS) was developed for the analysis of 27 pesticides, commonly used in Alsace, in atmospheric samples (particle and gas phases). As pesticides are expected to be present at very low concentrations and in a complex matrix, the analytical method used was both highly selective and sensitive. These two properties were obtained by associating chromatography with ion-trap MS/MS. To develop this method, analysis of electron impact in single MS was first conducted to choose the parent ions of the pesticides studied. Among the 27 pesticides analysed, seven of them require a derivatisation step. This was the case of some ureas (chlorotoluron, diuron and isoproturon), phenoxy acids (2,4-dichlorophenoxyacetic acid, 4-chloro-2-methylphenoxyacetic acid and mecoprop) and of bromoxynil. The derivatisation was performed with success with pentafluorobenzylbromide. Then, a MS/MS method was optimised by parameters such as the radio frequency storage level and the collision-induced dissociation excitation voltage. Finally, a last step enabled the development of two calibrating programs based on the quantification of daughter ions for the 20 pesticides analysed directly (run 1) and for the seven pesticides which needed derivatisation (run 2). With this analytical procedure, the detection limits varied between 2.5 and 1,250 pg m(-3) depending on the compounds studied. This method was tested with success for atmospheric samples collected in Strasbourg (France) during intensive pesticide treatment in 2002.

Atmosphere↗

Microwave assisted digestion of atmospheric aerosol samples followed by inductively coupled plasma mass spectrometry determination of trace elements.

A microwave digestion method in a closed vessel was developed for the determination of trace metals in atmospheric aerosols using inductively coupled plasma mass spectrometry (ICP-MS). A recovery study for the elements V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Cd, Sb, and Pb was conducted using multi-elemental standard solutions, NIST 1633b Trace Elements in Coal Fly Ash, and NIST 1648 Urban Particulate Matter. A simple digestion method using only HNO3/H2O2 gave good recoveries (90%-108%) for all elements except Cr in SRM 1648, but yielded low recoveries for SRM 1633b. A more robust method using HNO3/H2O2/HF/H3BO3 yielded higher recoveries (82%-103%) for the lighter elements (V-Zn) in SRM 1633b, and improved the Cr recovery in SRM 1648, but decreased the Se recovery in both SRMs. A comparative analysis of aerosol samples obtained at a remote mountain location Nathiagali, Pakistan (2.5 km above mean sea level), and Mayville, New York, downwind from the highly industrialized Midwestern United States, was carried out using Instrumental Neutron Activation Analysis (INAA) for the elements Cr, Mn, Fe, Co, Zn, As, Se, and Sb. The simple digestion method yielded excellent agreement for Cr, Fe, Zn, As, Se, and Sb, with slopes of the ICP-MS vs. INAA regressions of 0.90-1.00 and R2 values of 0.96-1.00. The regressions for Mn and Co had slopes of 0.82 and 0.84 with R2 values of 0.83 and 0.82, respectively. Addition of HF/H3BO3 did not improve the correlation for any of the elements and degraded the precision somewhat. The technique provides sensitivity and accuracy for trace elements in relatively small aerosol samples used in atmospheric chemistry studies related to SO2 oxidation in cloud droplets. The ability to determine concentrations of a very large number of elements from a single analysis will permit source apportionment of various trace pollutants and hence strategies to control the sources of air pollution. This is particularly important as the health effects of particulate matter are increasingly recognized.

Aerosols↗

Experimental human exposure to N,N-dimethylbenzylamine: generation of a controlled atmosphere and biological monitoring.

The aim of the present study was to develop a method for generation of dimethylbenzylamine (DMBA) atmospheres in an exposure chamber and to investigate the possibility of using urinary DMBA metabolites for biological monitoring of exposure to DMBA. A DMBA atmosphere was generated by use of the gas-permeation principle. Six health male volunteers were exposed for 8 h to DMBA at air levels of 20, 45, and 80 microns/m3. Air levels of DMBA were analyzed by gas chromatography (GC). The total urinary amount of DMBA (U-SumDMBA; DMBA and metabolites that can be reduced to DMBA, e.g., DMBAO) was analyzed using GC-mass spectrometry (MS). The exposure chamber maintained very low (0-130 micrograms/m3) and steady concentrations for several weeks. DMBA uptake by inhalation was 76%. The amine was quickly distributed and biotransformed to nearly 100%. DMBA was eliminated in the urine with a half-time of 4.3 h. More than 50% was eliminated within 2 h of exposure. However, at all exposure levels the subjects continued to excrete DMBA the next morning. There was a significant correlation between the exposure to DMBA and the U-SumDMBA. Thus, U-SumDMBA may become an important biomarker for monitoring of industrial exposure to DMBA.

Adult↗

The interacting effects of elevated atmospheric CO2 concentration, drought and leaf-to-air vapour pressure deficit on ecosystem isoprene fluxes.

Isoprene is the most abundant biogenic hydrocarbon released from vegetation and it plays a major role in tropospheric chemistry. Because of its link to climate change, there is interest in understanding the relationship between CO2, water availability and isoprene emission. We explored the effect of atmospheric elevated CO2 concentration and its interaction with vapour pressure deficit (VPD) and water stress, on gross isoprene production (GIP) and net ecosystem exchange of CO2 (NEE) in two Populus deltoides plantations grown at ambient and elevated atmospheric CO2 concentration in the Biosphere 2 Laboratory facility. Although GIP and NEE showed a similar response to light and temperature, their responses to CO2 and VPD were opposite; NEE was stimulated by elevated CO2 and depressed by high VPD, while GIP was inhibited by elevated CO2 and stimulated by high VPD. The difference in response between isoprene production and photosynthesis was also evident during water stress. GIP was stimulated in the short term and declined only when the stress was severe, whereas NEE started to decrease from the beginning of the experiment. This contrasting response led the carbon lost as isoprene in both the ambient and the elevated CO2 treatments to increase as water stress progressed. Our results suggest that water limitation can override the inhibitory effect of elevated CO2 leading to increased global isoprene emissions in a climate change scenario with warmer and drier climate.

Atmosphere↗

Hemiparasite abundance in an alpine treeline ecotone increases in response to atmospheric CO(2) enrichment.

Populations of the annual hemiparasites Melampyrum pratense L. and Melampyrum sylvaticum L. were studied at the treeline in the Swiss Alps after 3 years of in situ CO(2) enrichment. The total density of Melampyrum doubled to an average of 44 individuals per square meter at elevated CO(2) compared to ambient CO(2). In response to elevated CO(2), the height of the more abundant and more evenly distributed M. pratense increased by 20%, the number of seeds per fruit by 21%, and the total seed dry mass per fruit by 27%, but the individual seed size did not change. These results suggest that rising atmospheric CO(2) may stimulate the reproductive output and increase the abundance of Melampyrum in the alpine treeline ecotone. Because hemiparasites can have important effects on community dynamics and ecosystem processes, notably the N cycle, changing Melampyrum abundance may potentially influence the functioning of alpine ecosystems in a future CO(2)-rich atmosphere.

Atmosphere↗

Soil respiration in northern forests exposed to elevated atmospheric carbon dioxide and ozone.

The aspen free-air CO2 and O3 enrichment (FACTS II-FACE) study in Rhinelander, Wisconsin, USA, is designed to understand the mechanisms by which young northern deciduous forest ecosystems respond to elevated atmospheric carbon dioxide (CO2) and elevated tropospheric ozone (O3) in a replicated, factorial, field experiment. Soil respiration is the second largest flux of carbon (C) in these ecosystems, and the objective of this study was to understand how soil respiration responded to the experimental treatments as these fast-growing stands of pure aspen and birch + aspen approached maximum leaf area. Rates of soil respiration were typically lowest in the elevated O3 treatment. Elevated CO2 significantly stimulated soil respiration (8-26%) compared to the control treatment in both community types over all three growing seasons. In years 6-7 of the experiment, the greatest rates of soil respiration occurred in the interaction treatment (CO2 + O3), and rates of soil respiration were 15-25% greater in this treatment than in the elevated CO2 treatment, depending on year and community type. Two of the treatments, elevated CO2 and elevated CO2 + O3, were fumigated with 13C-depleted CO2, and in these two treatments we used standard isotope mixing models to understand the proportions of new and old C in soil respiration. During the peak of the growing season, C fixed since the initiation of the experiment in 1998 (new C) accounted for 60-80% of total soil respiration. The isotope measurements independently confirmed that more new C was respired from the interaction treatment compared to the elevated CO2 treatment. A period of low soil moisture late in the 2003 growing season resulted in soil respiration with an isotopic signature 4-6 per thousand enriched in 13C compared to sample dates when the percentage soil moisture was higher. In 2004, an extended period of low soil moisture during August and early September, punctuated by a significant rainfall event, resulted in soil respiration that was temporarily 4-6 per thousand more depleted in 13C. Up to 50% of the Earth's forests will see elevated concentrations of both CO2 and O3 in the coming decades and these interacting atmospheric trace gases stimulated soil respiration in this study.

Acer↗

Influence of wind direction on pollen concentration in the atmosphere.

The daily pollen concentration in the atmosphere of Badajoz (SW Spain) was analysed over a 6-year period (1993-1998) using a volumetric aerobiological trap. The results for the main pollination period are compared with the number of hours of wind each day in the four quadrants: 1 (NE), 2 (SE), 3 (SW) and 4 (NW). The pollen source distribution allowed 16 pollen types to be analysed as a function of their distribution in the four quadrants with respect to the location of the trap. Four of them correspond to species growing in an irrigated farmland environment (Amaranthaceae-Chenopodiaceae, Plantago, Scirpus, and Typha), five to riparian and woodland species (Salix, Fraxinus, Alnus, Populus, and Eucalyptus), four to urban ornamentals (Ulmus, Arecaceae, Cupressaceae, and Casuarina), and three which include the most frequent pollen grains of widely distributed species (Poaceae, Quercus, and Olea). The results show that the distribution of the sources and the wind direction play a very major role in determining the pollen concentration in the atmosphere when these sources are located in certain quadrants, and that the widely distributed pollen sources show no relationship with wind direction. In some years the values of the correlations were not maintained, which leads one to presume that, in order to draw significant conclusions and establish clear patterns of the influence of wind direction, a continuous and more prolonged study will be required.

Atmosphere↗

Relationship between atmospheric pressure and mortality in the Madrid Autonomous Region: a time-series study.

This study set out to determine the possible influence of variations in atmospheric pressure on mortality in the Madrid Autonomous Region (MAR), taking into account the possible confounding effect of other atmospheric variables. The study was based on daily mortality data from the MAR Revenue and Excise Authority, meteorological data from Getafe Observatory and air pollution data from the Madrid Municipal Automatic Air Pollution Monitoring Grid. A time-series analysis was performed, using Box-Jenkins modelling and controlling for the respective confounding variables. Furthermore, the different variables studied (pressure, temperature, pollutants, etc.) were used to produce a multivariate model of the different causes of mortality. A significant association was found between anticyclonic trend and mortality with circulatory causes in the medium-long term and anticyclonic trend and mortality with respiratory causes in the long term.

Air Pollution↗

The effects of extra-low-frequency atmospheric pressure oscillations on human mental activity.

Slight atmospheric pressure oscillations (APO) in the extra-low-frequency range below 0.1 Hz, which frequently occur naturally, can influence human mental activity. This phenomenon has been observed in experiments with a group of 12 healthy volunteers exposed to experimentally created APO with amplitudes 30-50 Pa in the frequency band 0.011-0.17 Hz. Exposure of the subjects to APO for 15-30 min caused significant changes in attention and short-term memory functions, performance rate, and mental processing flexibility. The character of the response depended on the APO frequency and coherence. Periodic APO promoted purposeful mental activity, accompanied by an increase in breath-holding duration and a slower heart rate. On the other hand, quasi-chaotic APO, similar to the natural perturbations of atmospheric pressure, disrupted mental activity. These observations suggest that APO could be partly responsible for meteorosensitivity in humans.

Adult↗

Long-term atmospheric mercury wet deposition at Underhill, Vermont.

Section 112(m) of the 1990 Clean Air Act Amendments, referred to as the Great Waters Program, mandated an assessment of atmospheric deposition of hazardous air pollutants (HAPs) to Lake Champlain. Mercury (Hg) was listed as a priority HAP and has continued to be a high priority for a number of national and international programs. An assessment of the magnitude and seasonal variation of atmospheric Hg levels and deposition in the Lake Champlain basin was initiated in December 1992 which included event precipitation collection, as well as collection of vapor and particle phase Hg in ambient air. Sampling was performed at the Proctor Maple Research Center in Underhill Center, VT. The range in the annual volume-weighted mean concentration for Hg in precipitation was 7.8-10.5 ng/l for the 11-year sampling period and the average amount of Hg deposited with each precipitation event was 0.10 microg/m2. The average amount of Hg deposited through precipitation each year from 1993 to 2003 was 9.7 microg/m2/yr. A seasonal pattern for Hg in precipitation is clearly evident, with increased Hg concentrations and deposition observed during spring and summer months. While a clear trend in the 11-year event deposition record at Underhill was not observed, a significant decrease in the event max-to-monthly ratio was observed suggesting that a major source influence was controlled over time. Discrete precipitation events were responsible for significant fractions of the monthly and annual loading of Hg to the forested ecosystem in Vermont. Monthly-averaged temperatures were found to be moderately correlated with monthly volume-weighted mean Hg concentrations (r2 = 0.61) and Hg deposition (r2 = 0.67) recorded at the Vermont site. Meteorological analysis indicated the highest levels of Hg in precipitation were associated with regional transport from the west, southwest, and south during the warmer months.

Air Pollutants↗

Simultaneous measurements of atmospheric pollutants and visibility with a Long-Path DOAS system in urban areas.

In this paper, the applicability of a Long-Path Differential Optical Absorption Spectroscopy (LP-DOAS) system was checked for the feasibility of the simultaneous measurement of trace gases (such as 03, NO2, SO2, and HCHO) and atmospheric visibility (light extinction by aerosols) in Asian urban areas. Field studies show that an LP-DOAS system can simultaneously measure the key pollutants (such as O3, NO2, SO2, and HCHO) at detection limits in the ppb/sub-ppb range as well as the Mie extinction coefficient with an uncertainty of approximately 0.1 km(-1) at time resolution of a few minutes. It is thus concluded that the use of LP-DOAS system is feasible for simultaneous measurement of gaseous pollutants as well as an atmospheric extinction coefficient which is tightly bound to fine particulate concentration.

Aerosols↗

Chemical composition of atmospheric aerosol (PM10) at a semi-arid urban site: influence of terrestrial sources.

Atmospheric aerosol (PM(10)) measurements were made at a regional representative semi-arid urban site, Tirupati, India over one-year period i.e. from October, 2001 to September, 2002. The samples were collected on polyflex filters, and analyzed for the major water-soluble ions - F, Cl, NO(3), SO(4), Na, NH(4), K, Ca and Mg, employing ion chromatograph. The average mass of PM(10) is found to be 32.75 mug/m(3) with a total water-soluble aerosol load (total anion + total cation) of 13.56 mug/m(3). Composition of aerosol showed higher concentration of SO(4) followed by Na, Ca and NO(3). Very good correlation is observed between crustal ions Ca and Mg (r=0.82) as well as between crustal and acidic ions; Ca and SO(4) (r=0.75) and NO(3) (r=0.67) and Mg and NO(3) (r=0.78) and SO(4) (r=0.73), suggest that the ionic composition was influenced by local terrestrial sources. The presence of SO(4) and NO(3) may be due to re-suspension of soil particles (formation by heterogeneous oxidation). Ca, Mg and Na are mainly soil derived ones. Correlation matrix with meteorological factors, as well as seasonal distribution of PM(10) and its ionic components present a clear trend of higher concentrations during summer due to greater particle release and lowering atmospheric levels during the rainy season due to washout effect. ANOVA results showed the significant variation of composition from season to season. Paired comparisons (DMRT) revealed the occurrence of significant difference in pairs of mean concentration from season to season except within monsoon i.e. between S-W and N-E monsoon.

Aerosols↗

Applicability of Henry's law to hydrogen, helium, and nitrogen solubilities in water and olive oil at 37 degrees C and pressures up to 300 atmospheres.

The solubilities of pure hydrogen, helium, and nitrogen in water and olive oil were measured at 37 degrees C at gas-saturation pressures from 25 to 300 atmospheres. Rigorous thermodynamic criteria were used to assess the applicability of Henry's law to the pressure dependence of the gas solubility in each system. The solubilities of the three gases in water and helium in olive oil followed Henry's law as given by the Krichevsky-Kasarnovsky equation. In contrast, hydrogen and nitrogen in olive oil each attained concentrations high enough to cause significant concentration-dependent variations of the dissolved gas activity coefficient and/or partial molal volume. The consequent deviations from Henry's law were greatest in the nitrogen-oil system, where mole fraction nitrogen solubilities calculated from the Krichevsky-Kasarnovsky equation exceeded measured values by 8, 14, and 23% at 50, 100, and 250 atm, respectively. Incorporation of results into the critical volume model of nitrogen anesthesia, using olive oil as a model of the physiological anesthetic site and literature data for the anesthetic potency of nitrogen in mice breathing high-pressure He-N2-O2 atmospheres, shows that nonideal solution behavior may become important for gases dissolved in physiological hydrophobic regions at biologically active concentrations, even if dissolved gas binding to proteins or other macromolecules is not involved.

Atmospheric Pressure↗

Freeze-drying of Streptococcus thermophilus: a comparison between the vacuum and the atmospheric method.

Frozen suspensions of Streptococcus thermophilus were freeze-dried in a vacuum or a fluidized adsorbent bed at atmospheric pressure. Optimum operating conditions for each process were defined. For the duration of processing and survival rate of bacteria, in each case vacuum freeze-drying seemed more satisfactory than atmospheric pressure freeze-drying. The use of reconstituted skimmed milk as a suspension medium provides good protection for S. thermophilus.

Atmospheric Pressure↗