G. Lambert

Evidence for marine production of isoprene

New data obtained in the Mediterranean Sea and Pacific Ocean show that isoprene could be produced in sea water by biological processes, leading to concentrations in the ppb range (10−9 liter of gas per liter of water). Taking into account Henrys constant for isoprene in water and the very low concentrations measured in the marine atmosphere, the superficial sea water is supersaturated in isoprene by one or two orders of magnitude. From these observations, an oceanic flux of the order of 1.2 Mt per year of isoprene can be estimated. This is a small value, as compared with the marine fluxes of the other NMHC; it is also practically negligible in the global burden of isoprene. However, because of its short lifetime in air, isoprene in remote marine atmosphere, entirely originates from superficial seawater, it could be therefore an useful tracer of marine emissions of gaseous compounds.

The marine source of C2-C6 aliphatic hydrocarbons

C2-C6 Nonmethane hydrocarbon (NMHC) concentrations in the atmospheric boundary layer and in surface seawater were simultaneously measured during an oceanographic cruise in the intertropical Indian Ocean. NMHC were found to be mainly C2-C4 alkenes and C2-C3 alkanes. Their concentrations ranged from 1 to 30×10−9 l/l in the seawater and 0.1 to 15 ppbv in the atmosphere. Seawater appeared to be a source because the C2-C6 NMHC were supersaturated with respect to the atmosphere by 2 or 3 orders of magnitude.After a selection of the pure marine atmospheric samples, performed with the help of stable and radioactive continental tracers, we found an identical composition in NMHC of surface air and seawater. This observation enabled us to establish that the gas transfer between sea and air occurred according to nonsteady state processes, and that the fluxes cannot be deduced only from atmospheric measurements. An order of magnitude value of the oceanic source for the different NMHC is however derived from the comparison of their sea water concentrations to that of propane and an independent evluation of the marine source of this last compound.

Volcanic emission of radionuclides and magma dynamics

210Pb,210Bi and210Po, the last decay products of the238U series, are highly enriched in volcanic plumes, relative to the magma composition. Moreover this enrichment varies over time and from volcano to volcano. A model is proposed to describe 8 years of measurements of Mt. Etna gaseous emissions. The lead and bismuth coefficients of partition between gaseous and condensed phases in the magma are determined by comparing their concentrations in lava flows and condensated volatiles. In the case of volatile radionuclides, an escaping time is calculated which appears to be related to the volcanic activity. Finally, it is shown that that magma which is degassing can already be partly degassed; it should be considered as a mixture of a few to 50% of deep non-degassed magma with a well degassed superficial magma cell.

Nonmethane hydrocarbons in an oceanic atmosphere

C2−C6 Nonmethane hydrocarbons (NMHC) and radioactive continental tracers were measured during two oceanographic cruises, in June 1982 in the Mediterranean and Red Sea, and in November 1982 across the North Atlantic and South Pacific oceans. Typical concentrations in marine atmosphere are between 0.05 and 0.2 ppbv. Owing to their similar lifetimes, propane and radon-222 are found to be well correlated. This relationship establishes that propane is mainly produced over lands and enables us to estimate its continental source strength at about 60×106 tons of carbon per year.

Volcanic output of SO2 and trace metals: A new approach

Owing to a model of volcanic emission of gases and volatiles, it was possible to normalize to 210Po the volcanic output of SO2, Pb, Bi and other trace as well as major metals. It appears that the results concerning SO2, Pb and Bi agree with previous estimates derived on a very different basis. The evaluation was extended to Cd, Cu, Zn, Al, Mg, Na and K. Moreover, it was observed that, even for poorly volatile major metals, the part of volcanic aerosols produced by evaporation is at least comparable to that which results from spattering.

Fractionation of metals in volcanic emissions

Abstract The enrichment of some metals (Al, Mg, Na, K, Cu, Zn, Cd) in volcanic gases is measured by an emanation coefficient ex relating the amount of the element x in lavas and in aerosols.ex is determined in the volcanic emissions of Mount Etna (Sicily), with regard to that of210Pb. The accuracy of the results is limited by the geochemical behavior of common lead compared to that of210Pb. Concerning the most volatile species, it appears that practically all the volcanic aerosols are produced by evaporation followed by gas-to-particle conversion and the spattered fraction appears to be negligible.

Fractionation of families of major, minor, and trace metals across the melt-vapor interface in volcanic exhalations☆

Chemical families of metals fractionate systematically as they pass from a silicate melt across the interface with the vapor phase and on into a cooled volcanic plume. We measured three groups of metals in a small suite of samples collected on filters from the plumes of Kilauea (Hawaii, USA), Etna (Sicily), and Merapi (Java) volcanoes. These were the major, minor, and trace metals of the alkali and alkaline earth families (K, Rb, Cs, Ca, Sr, Ba), a group of ordinarily rare metals (Cd, Cu, In, Pb, Tl) that are related by their chalcophile affinities, and the radon daughter nuclides 210Po, 210Bi, and 210Pb. The measurements show the range and some details of systematic melt-vapor fractionation within and between these groups of metals. In the plumes of all three volcanoes, the alkali metals are much more abundant than the alkaline earth metals. In the Kilauea plume, the alkali metals are at least six times more abundant than the alkaline earth metals, relative to abundances in the melt; at Etna, the factor is at least 300. Fractionations within each family are, commonly, also distinctive; in the Kilauea plume, in addition to the whole alkaline earth family being depleted, the heaviest metals of the family (Sr, Ba) are progressively more depleted than the light metal Ca. In plumes of fumaroles at Merapi, K/Cs ratios were approximately three orders of magnitude smaller than found in other earth materials. This may represent the largest observed enrichment of the “light ion lithophile” (LIL) metals. Changes in metal ratios were seen through the time of eruption in the plumes of Kilauea and Etna. This may reflect degree of degassing of volatiles, with which metals complex, from the magma bodies. At Kilauea, the changes in fractionation were seen over about three years; fractionation within the alkaline earth family increased, and that between the two families decreased, over that time. All of the ordinarily rare chalcophile metals measured are extremely abundant in volcanic plumes, and Cd and Tl are enriched relative to the others. Indium is much more abundant in the plume of the hotspot volcano Kilauea than in the Etna plume (probably non-hotspot in character). It may be a useful indicator of the tapping of deep mantle zones, or could aid in the interpretation of reports of Pt group metals in exhalations from hot spot volcanoes. Indium in old glacial ice strata could help assess magnitude and variability of exhalations from hotspot volcanoes in past time. Strong melt-vapor fractionation of the alkali and alkaline earth metals may only be observed in plumes during quiescent degassing of volcanoes; when large amounts of ash or spatter (undifferentiated lava) enter the plume, its alkali and alkaline earth metal composition may approach that of the melt. Ratios among the chalcophile metals may not be much changed by addition of ash, because their concentrations in melt are so small, and masses of them in any plume may remain dominated by transfer across the melt-vapor interface. Radon daughter nuclides give information about state of volcanic activity at time of sampling. The precisely known origins, ultratrace detectability, decay systematics, and wide variations in volatility of these species provide information about residence times, degassing and travel histories, and identities of melt bodies in volcanic systems.

Radon daughters and sulfur output from Erebus volcano, Antarctica

The 1977–1978 French New-Zealand summer campaign at Mount Erebus took place during a period of rather low activity. In such conditions, we could measure an output of 3 Ci of 210Pb, 100 Ci of 210Po and 1010 tons of sulfate per year. The 210Po seems to be the only element emitted by Mount Erebus whose contribution to the Antarctic atmosphere is significant: sulfur compounds as well as radon emitted by Mount Erebus during a period of quiescent activity, have a negligible contribution to the overall Antarctic budgets. The presence of long-lived radon daughters in volcanic gases, highly enriched in volatile elements, seems to be a characteristic of gases emitted directly from the magma at high temperature.

NMHC in the marine atmosphere: Preliminary results of monitoring at Amsterdam Island

Between January 1984 and May 1987, C2 to C5 NMHC concentrations, and Radon-222 activities were measured at Amsterdam Island in the Indian Ocean. A large variability of about one order of magnitude was observed in the NMHC concentrations. Most of the samples were collected under marine influence. Using ethene as a reference compound for marine emissions, it appears that the NMHC/ethene composition of the air and its variability directly reflect the composition of dissolved gases in surface seawater. Only the ethane/ethene ratio presents a significant deviation from this typical composition and this can be attributed to a continental component. At sea level, the reation frequency of OH radicals with the NMHC is similar to that of methane and carbon monoxide. Thus, the contribution of marine NMHC should be taken into account in the modelling of oxidants in remote atmospheres.

TROPOZ II: Global distributions and budgets of methane and light hydrocarbons

One hundred atmospheric samples were collected aboard the French Caravelle research aircraft, during the TROPOZ II experiment (January 1991). Tropospheric meridional distributions versus height were then derived from 70° N to 60° S and between 0.25 km and 11 km for methane, acetylene, ethane and propane. Areas of significant emissions were identified over northern latitudes with, for acetylene, maximum mixing ratios in the north (1.896 ppbv) more than 70 times higher than in background southern latitudes (0.025 ppbv). The influence of emissions from biomass burning was also obvious in the tropical boundary layer. Significant dynamic phenomena led to high mixing ratio zones above 8 or 10 km even for the most reactive hydrocarbons.For the first time, simultaneous assessment of global tropospheric contents of several light hydrocarbons was carried out. Using TROPOZ II data (January 1991) and STRATOZ III data (June 1984) collected by Rudolph (1988) during similar aircraft flights in 1988, the following tropospheric loads (in Tg-compound) were estimated, in January 1991 and June 1984, respectively: 1.1 and 0.4 for acetylene, 5.0 and 3.9 for ethane, 3.6 and 1.4 for propane and 3545 for methane in January only. According to our results, 40 to 65% of acetylene and alkanes are oxidized in the tropics. In addition, by computing the annual tropospheric sink of acetylene and alkanes, an evaluation of their annual global fluxes was performed. The figures are, in Tg-compound y-1 with an uncertainty of 80% to an order of magnitude, based on January and June data, respectively: 10 and 6.6 for acetylene, 16.3 and 17.6 for ethane and 52.3 and 26.5 for propane.