Analysis of the spatial and temporal changes in soil CO<Subscript>2</Subscript> flux in alpine meadow of Qilian Mountain

Field experiments on the CO₂ flux of alpine meadow soil in the Qilian Mountain were conducted along the elevation gradient during the growing season of 2004 and 2005. The soil CO₂ flux was measured using the Li-6400-09 soil respiration chamber attached to the Li-6400 portable photosynthesis system. The effects of water and heat and roots on the soil CO₂ flux were statistically analyzed. The results show that soil CO₂ flux along the elevation gradient gradually decreases. The soil CO₂ flux was low at night, with lowest value occurring between 0200 and 0600 hours, started to rise rapidly during 0700–0830 hours, and then descend during 1600–1830 hours. The peak CO₂ efflux appears during 1100–1600 hours. The diurnal average of soil CO₂ efflux was between 0.56 ± 0.32 and 2.53 ± 0.76 μmol m⁻² s⁻¹. Seasonally, soil CO₂ fluxes are relatively high in summer and autumn and low in spring and winter. The soil CO₂ efflux, from the highest to the lowest in the ranking order, occurred in July and August (4.736 μmol m⁻² s⁻¹), June and September, and May and October, respectively. The soil CO₂ efflux during the growing season is positively correlated with soil temperature, root biomass and soil water content.     

Dynamics of CO<Subscript>2</Subscript> fluxes and concentrations during a shallow subsurface CO<Subscript>2</Subscript> release

A field facility located in Bozeman, Montana provides the opportunity to test methods to detect, locate, and quantify potential CO₂ leakage from geologic storage sites. From 9 July to 7 August 2008, 0.3 t CO₂ day⁻¹ were injected from a 100-m long, ~2.5-m deep horizontal well. Repeated measurements of soil CO₂ fluxes on a grid characterized the spatio-temporal evolution of the surface leakage signal and quantified the surface leakage rate. Infrared CO₂ concentration sensors installed in the soil at 30 cm depth at 0–10 m from the well and at 4 cm above the ground at 0 and 5 m from the well recorded surface breakthrough of CO₂ leakage and migration of CO₂ leakage through the soil. Temporal variations in CO₂ concentrations were correlated with atmospheric and soil temperature, wind speed, atmospheric pressure, rainfall, and CO₂ injection rate.     

Effects of nitrogen on the ecosystem respiration,CH<Subscript>4</Subscript> and N<Subscript>2</Subscript>O emissions to the atmosphere from the freshwater marshes in northeast China

Freshwater marshes could be a source of greenhouse gases emission because they contain large amounts of soil carbon and nitrogen. These emissions are strongly influenced by exogenous nitrogen. We investigate the effects of exogenous nitrogen on ecosystem respiration (CO₂), CH₄ and N₂O emissions from freshwater marshes in situ in the Sanjiang Plain Northeast of China during the growing seasons of 2004 and 2005, using a field fertilizer experiment and the static opaque chamber/GC techniques. The results show that there were no significant differences in patterns of seasonal variations of CO₂ and CH₄ among the fertilizer and non-fertilizer treatments, but the seasonal patterns of N₂O emission were significantly influenced by the exogenous nitrogen. Seasonal averages of the CO₂ flux from non-fertilizer and fertilizer were 987.74 and 1,344.35 mg m ⁻² h ⁻¹, respectively, in 2004, and 898.59 and 2,154.17 mg m ⁻² h ⁻¹, respectively, in 2005. And the CH₄ from the control and fertilizer treatments were 6.05 and 13.56 mg m ⁻² h ⁻¹ and 0.72 and 1.88 mg m ⁻² h ⁻¹, respectively, in 2004 and 2005. The difference of N₂O flux between the fertilizer and non-fertilizer treatments is also significant either in 2004 and 2005. On the time scale of 20-, 100-, and 500-year periods, the integrated global warming potential (GWP) of CO₂ + CH₄ + N₂O released during the two growing seasons for the treatment of fertilizer was 97, 94 and 89%, respectively, higher than that for the control, which suggested that the nitrogen fertilizer can enhance the GWP of the CH₄ and N₂O either in long time or short time scale.     

Application of the <Superscript>137</Superscript>Cs tracer technique to study soil erosion of alpine meadows in the headwater region of the Yellow River

The ¹³⁷Cs tracer technique was used to study soil erosion of alpine meadow grassland in two small river basins in the headwater region of the Yellow River. The results show that the levels of ¹³⁷Cs in soil samples from this alpine meadow vegetation zone exhibit an exponential distribution, generally within a depth of approximately 20 cm. Due to strong winds, freeze-thaw cycles and water, soil erosion was found to be stronger on the upper slope than on the lower slope, and except for the slope crest, the intensity of soil erosion at other sites was as follows: upslope < midslope < downslope. There was a significant negative correlation between the intensity of soil erosion and the extent of alpine meadow vegetation cover (P < 0.01). The mean soil erosion modulus exhibited a linear reduction trend with an increase in vegetation cover, and the correlation coefficient R ² was ≥ 0.997. The higher the degradation degree of the alpine meadow grassland, the greater is the soil erosion. The mean erosion modulus in the severely degraded meadow zone was 2.23 times greater than the one in the slightly degraded zone, and the maximum erosion modulus reached 2.96 × 10⁶ kg/km²/a.     

Diel Aquatic CO<Subscript>2</Subscript> System Dynamics of a Bermudian Mangrove Environment

Mangrove ecosystems play an important, but understudied, role in the cycling of carbon in tropical and subtropical coastal ocean environments. In the present study, we examined the diel dynamics of seawater carbon dioxide (CO₂) and dissolved oxygen (DO) for a mangrove-dominated marine ecosystem (Mangrove Bay) and an adjacent intracoastal waterway (Ferry Reach) on the island of Bermuda. Spatial and temporal trends in seawater carbonate chemistry and associated variables were assessed from direct measurements of dissolved inorganic carbon, total alkalinity, dissolved oxygen (DO), temperature, and salinity. Diel pCO₂ variability was interpolated across hourly wind speed measurements to determine variability in daily CO₂ fluxes for the month of October 2007 in Bermuda. From these observations, we estimated rates of net sea to air CO₂ exchange for these two coastal ecosystems at 59.8 ± 17.3 in Mangrove Bay and 5.5 ± 1.3 mmol m⁻² d⁻¹ in Ferry Reach. These results highlight the potential for large differences in carbonate system functioning and sea-air CO₂ flux in adjacent coastal environments. In addition, observation of large diel variability in CO₂ system parameters (e.g., mean pCO₂: 390–2,841 μatm; mean pH_T: 8.05–7.34) underscores the need for careful consideration of diel cycles in long-term sampling regimes and flux estimates.     

First-principles-based calculations of the CaCO<Subscript>3</Subscript>–MgCO<Subscript>3</Subscript> and CdCO<Subscript>3</Subscript>–MgCO<Subscript>3</Subscript> subsolidus phase diagrams

 Planewave pseudopotential calculations of supercell total energies were used as bases for first-principles calculations of the CaCO₃–MgCO₃ and CdCO₃–MgCO₃ phase diagrams. Calculated phase diagrams are in qualitative to semiquantitative agreement with experiment. Two unobserved phases, Cd₃Mg (CO₃)₄ and CdMg₃(CO₃)₄, are predicted. No new phases are predicted in the CaCO₃–MgCO₃ system, but a low-lying metastable Ca₃Mg(CO₃)₄ state, analogous to the Cd₃Mg(CO₃)₄ phase is predicted. All of the predicted lowest-lying metastable states, except for huntite CaMg₃(CO₃)₄, have dolomite-related structures, i.e. they are layer structures in which A _m B _n cation layers lie perpendicular to the rhombohedral [111] vector. Received: 6 May 2002 / Accepted: 23 October 2002 Acknowledgements This work was partially supported by NSF contract DMR-0080766 and NIST.     

Elasticity and equation of state of Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript>

A single crystal X-ray diffraction study on lithium tetraborate Li₂B₄O₇ (diomignite, space group I4₁ cd) has been performed under pressure up to 8.3 GPa. No phase transitions were found in the pressure range investigated, and hence the pressure evolution of the unit-cell volume of the I4₁ cd structure has been described using a third-order Birch–Murnaghan equation of state (BM-EoS) with the following parameters: V ₀  = 923.21(6) ų, K ₀  = 45.6(6) GPa, and K′ = 7.3(3). A linearized BM-EoS was fitted to the axial compressibilities resulting in the following parameters a ₀  = 9.4747(3) Å, K _0a  = 73.3(9) GPa, K′ _a  = 5.1(3) and c ₀  = 10.2838(4) Å, K _0c  = 24.6(3) GPa, K′ _c  = 7.5(2) for the a and c axes, respectively. The elastic anisotropy of Li₂B₄O₇ is very large with the zero-pressure compressibility ratio β _0c /β _0a  = 3.0(1). The large elastic anisotropy is consistent with the crystal structure: A three-dimensional arrangement of relatively rigid tetraborate groups [B₄O₇]²⁻ forms channels occupied by lithium along the polar c–axis, and hence compression along the c axis requires the shrinkage of the lithium channels, whereas compression in the a direction depends mainly on the contraction of the most rigid [B₄O₇]²⁻ units. Finally, the isothermal bulk modulus obtained in this work is in general agreement with that derived from ultrasonic (Adachi et al. in Proceedings-IEEE Ultrasonic Symposium, 228–232, 1985; Shorrocks et al. in Proceedings-IEEE Ultrasonic Symposium, 337–340, 1981) and Brillouin scattering measurements (Takagi et al. in Ferroelectrics, 137:337–342, 1992).     

CO<Subscript>2</Subscript> emissions from a municipal site for final disposal of solid waste in Gualeguaychu,Entre Rios Province,Argentina

This paper estimates CO₂ fluxes in a municipal site for final disposal of solid waste, located in Gualeguaychu, Argentina. Estimations were made using the accumulation chamber methods, which had been calibrated previously in laboratory. CO₂ fluxes ranged from 31 to 331 g m⁻² day⁻¹. Three different populations were identified: background soil gases averaging 46 g m⁻² day⁻¹, intermediate anomalous values averaging 110 g m⁻² day⁻¹ and high anomalous values averaging 270 g m⁻² day⁻¹. Gas samples to a depth of 20 cm were also taken. Gas fractions, XCO₂ < 0.1, XCH₄ < 0.01, XN₂ ~0.71 and XO₂ ~0.21, δ¹³C of CO₂ (−34 to −18‰), as well as age of waste emplacement, suggest that the study site may be at the final stage of aerobic biodegradation. In a first approach, and following the downstream direction of groundwater flow, alkalinity and δ¹³C of dissolved inorganic carbon (−15 to 4‰) were observed to increase when groundwater passed through the disposal site. This suggests that the CO₂ generated by waste biodegradation dissolves or that dissolved organic matter appears as a result of leachate degradation.     

CO<Subscript>2</Subscript> absorption by alkaline soils and its implication to the global carbon cycle

Motivated by the rapid increase in atmospheric CO₂ due to human activities since the Industrial Revolution, and the climate changes it produced, the world’s concerned scientific community has made a huge effort to investigate the global carbon cycle. However, the results reveal that the global CO₂ budget cannot be balanced, unless a “missing sink” is invoked. Although numerous studies claimed to find the “missing sink”, none of those claims has been widely accepted. This current study showed that alkaline soil on land are absorbing CO₂ at a rate of 0.3–3.0 μmol m⁻² s⁻¹ with an inorganic, non-biological process. The intensity of this CO₂ absorption is determined by the salinity, alkalinity, temperature and water content of the saline/alkaline soils, which are widely distributed on land. Further studies revealed that high salinity or alkalinity positively affected the CO₂ absorbing intensity, while high temperature and water content had a negative effect on the CO₂ absorbing intensity of these soils. This inorganic, non-biological process of CO₂ absorption by alkaline soils might have significant implications to the global carbon budget accounting.     

Respiration and Calcification of <Emphasis Type="Italic">Crassostrea gigas</Emphasis>: Contribution of an Intertidal Invasive Species to Coastal Ecosystem CO<Subscript>2</Subscript> Fluxes

Respiration and calcification rates of the Pacific oyster Crassostrea gigas were measured in a laboratory experiment in the air and underwater, accounting for seasonal variations and individual size, to estimate the effects of this exotic species on annual carbon budgets in the Bay of Brest, France. Respiration and calcification rates changed significantly with season and size. Mean underwater respiration rates, deducted from changes in dissolved inorganic carbon (DIC), were 11.4 μmol DIC g⁻¹ ash-free dry weight (AFDW) h⁻¹ (standard deviation (SD), 4.6) and 32.3 μmol DIC g⁻¹ AFDW h⁻¹ (SD 4.1) for adults (80–110 mm shell length) and juveniles (30–60 mm), respectively. The mean daily contribution of C. gigas underwater respiration (with 14 h per day of immersion on average) to DIC averaged over the Bay of Brest population was 7.0 mmol DIC m⁻² day⁻¹ (SD 8.1). Mean aerial CO₂ respiration rate, estimated using an infrared gas analyzer, was 0.7 μmol CO₂ g⁻¹ AFDW h⁻¹ (SD 0.1) for adults and 1.1 μmol CO₂ g⁻¹ AFDW h⁻¹ (SD 0.2) for juveniles, corresponding to a mean daily contribution of 0.4 mmol CO₂ m⁻² day⁻¹ (SD 0.50) averaged over the Bay of Brest population (with 10 h per day of emersion on average). Mean CaCO₃ uptake rates for adults and juveniles were 4.5 μmol CaCO₃ g⁻¹ AFDW h⁻¹ (SD 1.7) and 46.9 μmol CaCO₃ g⁻¹ AFDW h⁻¹ (SD 29.2), respectively. The mean daily contribution of net calcification in the Bay of Brest C. gigas population to CO₂ fluxes during immersion was estimated to be 2.5 mmol CO₂ m⁻² day⁻¹ (SD 2.9). Total carbon release by this C. gigas population was 39 g C m⁻² year⁻¹ and reached 334 g C m⁻² year⁻¹ for densely colonized areas with relative contributions by underwater respiration, net calcification, and aerial respiration of 71%, 25%, and 4%, respectively. These observations emphasize the substantial influence of this invasive species on the carbon cycle, including biogenic carbonate production, in coastal ecosystems.     

Seagrass Meadows Modify Drag Forces on the Shell of the Fan Mussel <Emphasis Type="Italic">Pinna nobilis</Emphasis>

We assess the sheltering effect of Posidonia oceanica meadows on drag forces exerted on shells of the fan mussel Pinna nobilis. We examine a range of shell sizes under four unidirectional flow speeds (0.05–0.34 m s⁻¹) and two oscillating regimes. Three meadow densities are evaluated and a control without vegetation. We found that the attenuating effect of the meadow on drag forces experienced by bivalves is determined by the form of the hydrodynamic energy, e.g., as unidirectional flow or wave action. In tidal currents, the meadow protects most sizes of bivalves, with a higher efficiency for dense meadows, while in wave dominant zones the meadow reduces drag forces for bivalves with shell areas below a threshold of 0.019 m², whereas larger animals experience increased drag forces within the meadow independent of meadow density. Reduction of shoot density in seagrass meadows might therefore not affect the effectiveness of the canopy to reduce drag forces on associated species like the fan mussel in wave-dominated areas while increased storm frequency could result into losses of larger individuals during periods of high wave action.     

Experimental study of pure and mixtures of CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> adsorption on modified carbon nanotubes

In this work 3-[2-(2-aminoethylamino)ethylamino]propyl trimethoxysilane (TRI) was employed to functionalize MWCNT containing hydroxyl groups (OH-MWCNT), and the XRD, FTIR, TGA and CHNS elemental analysis techniques were used to characterize the resulted adsorbents. The characterization results for amine-MWCNT showed amine groups effectively attached to the surface of the MWCNT. The equilibrium adsorption capacity of pure CO₂ and CH₄ and their binary mixture on the pristine MWCNT, OH-MWCNT and amine-MWCNT was measured through a set of equilibrium adsorption experiments at 303.2 and 318.2 K. Capacities of all three types of adsorbents for CO₂ adsorption were higher than those for methane adsorption. Also, amine-MWCNT demonstrated better performance on CO₂ adsorption than the other two adsorbents, especially at low partial pressures. The capacity of amine-MWCNT for pure CO₂ adsorption was 2.5 and 4 times as much as those for pristine MWCNT and OH-MWCNT, respectively, at the temperature of 303.2 K and the pressure of 0.2 bar. The binary adsorption experiment revealed that CO₂/CH₄ selectivity for pristine MWCNT and amine-MWCNT in all molar fractions of CO₂ is about 1.77 and 7, respectively.     

Relationship between soil CO<Subscript>2</Subscript> flux and volcanic tremor at Mt. Etna: Implications for magma dynamics

Large variations of the CO₂ flux through the soil were observed between November 2002 and January 2006 at Mt. Etna volcano. In many cases, the CO₂ flux was strongly influenced by changes in air temperature and atmospheric pressure. A new filtering method was then developed to remove the atmospheric influences on soil CO₂ flux and, at the same time, to highlight the variations strictly related to volcanic activity. Successively, the CO₂ corrected data were quantitatively compared with the spectral amplitude of the volcanic tremor by cross correlation function, cross-wavelet spectrum and wavelet coherence. These analyses suggested that the soil CO₂ flux variations preceded those of volcanic tremor by about 50 days. Given that volcanic tremor is linked to the shallow (a few kilometer) magma dynamics and soil CO₂ flux related to the deeper (~12 km b.s.l.) magma dynamics, the “delayed similarity” between the CO₂ flux and the volcanic tremor amplitude was used to assess the average speed in the magma uprising into the crust, as about 170–260 m per day. Finally, the large amount of CO₂ released before the onset of the 2004–2005 eruption indicated a deep ingression of new magma, which might have triggered such an eruption.     

Contribution of a Dense Population of the Brittle Star <Emphasis Type="Italic">Acrocnida brachiata</Emphasis> (Montagu) to the Biogeochemical Fluxes of CO<Subscript>2</Subscript> in a Temperate Coastal Ecosystem

The production of organic matter and calcium carbonate by a dense population of the brittle star Acrocnida brachiata (Echinodermata) was calculated using demographic structure, population density, and relations between the size (disk diameter) and the ash-free dry weight (AFDW) or the calcimass. During a 2-year survey in the Bay of Seine (Eastern English Channel, France), organic production varied from 29 to 50 g_AFDW m⁻² year⁻¹ and CaCO₃ production from 69 to 104 g_CaCO3 m⁻² year⁻¹. Respiration was estimated between 1.7 and 2.0 mol_CO2 m⁻² year⁻¹. Using the molar ratio (ψ) of CO₂ released: CaCO₃ precipitated, this biogenic precipitation of calcium carbonate would result in an additional release between 0.5 and 0.7 mol_CO2 m⁻² year⁻¹ that represented 23% and 26% of total CO₂ fluxes (sum of calcification and respiration). The results of the present study suggest that calcification in temperate shallow environments should be considered as a significant source of CO₂ to seawater and thus a potential source of CO₂ to the atmosphere, emphasizing the important role of the biomineralization (estimated here) and dissolution (endoskeletons of dead individuals) in the carbon budget of temperate coastal ecosystems.     

Time-lapse crosswell seismic and VSP monitoring of injected CO<Subscript>2</Subscript> in a brine aquifer

Seismic surveys successfully imaged a small scale CO₂ injection (1,600 ton) conducted in a brine aquifer of the Frio Formation near Houston, Texas. These time-lapse borehole seismic surveys, crosswell and vertical seismic profile (VSP), were acquired to monitor the CO₂ distribution using two boreholes (the new injection well and a pre-existing well used for monitoring) which are 30 m apart at a depth of 1,500 m. The crosswell survey provided a high-resolution image of the CO₂ distribution between the wells via tomographic imaging of the P-wave velocity decrease (up to 500 m/s). The simultaneously acquired S-wave tomography showed little change in S-wave velocity, as expected for fluid substitution. A rock physics model was used to estimate CO₂ saturations of 10–20% from the P-wave velocity change. The VSP survey resolved a large (∼70%) change in reflection amplitude for the Frio horizon. This CO₂ induced reflection amplitude change allowed estimation of the CO₂ extent beyond the monitor well and on three azimuths. The VSP result is compared with numerical modeling of CO₂ saturations and is seismically modeled using the velocity change estimated in the crosswell survey.     

Statistical evaluation of PM<Subscript>10</Subscript> and distribution of PM<Subscript>1</Subscript>, PM<Subscript>2.5</Subscript>, and PM<Subscript>10</Subscript> in ambient air due to extreme fireworks episodes (Deepawali festivals) in megacity Delhi

Temporal variation of PM₁₀ using 2-year data (January, 2007–December, 2008) of Delhi is presented. PM₁₀ varied from 42 to 200 μg m⁻³ over January to December, with an average 114.1 ± 81.1 μg m⁻³. They are comparable with the data collected by Central Pollution Control Board (National Agency which monitors data over the entire country in India) and are lower than National Ambient Air Quality (NAAQ) standard during monsoon, close to NAAQ during summer but higher in winter. Among CO, NO₂, SO₂, rainfall, temperature, and wind speed, PM₁₀ shows good correlation with CO. Also, PM₁₀, PM_2.5, and PM₁ levels on Deepawali days when fireworks were displayed are presented. In these festive days, PM₁₀, PM_2.5, and PM₁ levels were 723, 588, and 536 μg m⁻³ in 2007 and 501, 389, and 346 μg m⁻³ in 2008. PM₁₀, PM_2.5, and PM₁ levels in 2008 were 1.5 times lower than those in 2007 probably due to higher mixing height (446 m), temperature (23.8°C), and winds (0.36 ms⁻¹).     

Using hyperspectral plant signatures for CO<Subscript>2</Subscript> leak detection during the 2008 ZERT CO<Subscript>2</Subscript> sequestration field experiment in Bozeman,Montana

Hyperspectral plant signatures can be used as a short-term, as well as long-term (100-year timescale) monitoring technique to verify that CO₂ sequestration fields have not been compromised. An influx of CO₂ gas into the soil can stress vegetation, which causes changes in the visible to near-infrared reflectance spectral signature of the vegetation. For 29 days, beginning on July 9, 2008, pure carbon dioxide gas was released through a 100-m long horizontal injection well, at a flow rate of 300 kg day⁻¹. Spectral signatures were recorded almost daily from an unmown patch of plants over the injection with a “FieldSpec Pro” spectrometer by Analytical Spectral Devices, Inc. Measurements were taken both inside and outside of the CO₂ leak zone to normalize observations for other environmental factors affecting the plants. Four to five days after the injection began, stress was observed in the spectral signatures of plants within 1 m of the well. After approximately 10 days, moderate to high amounts of stress were measured out to 2.5 m from the well. This spatial distribution corresponded to areas of high CO₂ flux from the injection. Airborne hyperspectral imagery, acquired by Resonon, Inc. of Bozeman, MT using their hyperspectral camera, also showed the same pattern of plant stress. Spectral signatures of the plants were also compared to the CO₂ concentrations in the soil, which indicated that the lower limit of soil CO₂ needed to stress vegetation is between 4 and 8% by volume.     

Structure of magnetite (Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>) above the Curie temperature: a cation ordering study

A pristine magnetite (Fe₃O₄) specimen was studied by means of Neutron Powder Diffraction in the 273–1,073 K temperature range, in order to characterize its structural and magnetic behavior at high temperatures. An accurate analysis of the collected data allowed the understanding of the behavior of the main structural and magnetic features of magnetite as a function of temperature. The magnetic moments of both tetrahedral and octahedral sites were extracted by means of magnetic diffraction up to the Curie temperature (between 773 and 873 K). A change in the thermal expansion coefficient around the Curie temperature together with an increase in the oxygen coordinate value above 700 K can be observed, both features being the result of a change in the thermal expansion of the tetrahedral site. This anomaly is not related to the magnetic transition but can be explained with an intervened cation reordering, as magnetite gradually transforms from a disordered configuration into a partially ordered one. Based on a simple model which takes into account the cation-oxygen bond length, the degree of order as a function of temperature and consequently the enthalpy and entropy of the reordering process were determined. The refined values are ΔH⁰ = −23.2(1.7) kJ mol⁻¹ and ΔS⁰ = −16(2) J K⁻¹ mol⁻¹. These results are in perfect agreement with values reported in literature (Mack et al. in Solid State Ion 135(1–4):625–630, 2000; Wu and Mason in J Am Ceramic Soc 64(9):520–522, 1981).     

LiFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> and NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> at low temperatures: an infrared spectroscopic study

 Synthetic aegirine LiFeSi₂O₆ and NaFeSi₂O₆ were characterized using infrared spectroscopy in the frequency range 50–2000 cm⁻¹, and at temperatures between 20 and 300 K. For the C2/c phase of LiFeSi₂O₆, 25 of the 27 predicted infrared bands and 26 of 30 predicted Raman bands are recorded at room temperature. NaFeSi₂O₆ (with symmetry C2/c) shows 25 infrared and 26 Raman bands. On cooling, the C2/c–P2₁/c structural phase transition of LiFeSi₂O₆ is characterized by the appearance of 13 additional recorded peaks. This observation indicates the enlargement of the unit cell at the transition point. The appearance of an extra band near 688 cm⁻¹ in the monoclinic P2₁/c phase, which is due to the Si–O–Si vibration in the Si₂O₆ chains, indicates that there are two non-equivalent Si sites with different Si–O bond lengths. Most significant spectral changes appear in the far-infrared region, where Li–O and Fe–O vibrations are mainly located. Infrared bands between 300 and 330 cm⁻¹ show unusually dramatic changes at temperatures far below the transition. Compared with the infrared data of NaFeSi₂O₆ measured at low temperatures, the change in LiFeSi₂O₆ is interpreted as the consequence of mode crossing in the frequency region. A generalized Landau theory was used to analyze the order parameter of the C2/c–P2₁/c phase transition, and the results suggest that the transition is close to tricritical. Received: 21 January 2002 / Accepted: 22 July 2002     

Continuous in situ measurements of volcanic gases with a diode-laser-based spectrometer: CO<Subscript>2</Subscript> and H<Subscript>2</Subscript>O concentration and soil degassing at Vulcano (Aeolian islands: Italy)

We report on a continuous-measurement campaign carried out in Vulcano (Aeolian islands, Sicily), devoted to the simultaneous monitoring of CO₂ and H₂O concentrations. The measurements were performed with an absorption spectrometer based on a semiconductor laser source emitting around a 2-μm wavelength. The emitted radiation was selectively absorbed by two molecular ro-vibrational transitions specific of the investigated species. Data for CO₂ and H₂O concentrations, and CO₂ soil diffusive flux using an accumulation chamber configuration, were collected at several interesting sampling points on the island (Porto Levante beach- PLB, Fossa Grande Crater – FOG- and Valley of Palizzi, PAL). CO₂/H₂O values, measured on the ground, are very similar (around 0.019 (± 0.006)) and comparable to the previous discrete detected values of 0.213 (Fumarole F5-La Fossa crater rim) and 0.012 (Fumarole VFS – Baia Levante beach) obtaid during the 1977–1993 heating phase of the crater fumaroles.