Carbon dioxide diffuse emission from the soil: ten years of observations at Vesuvio and Campi Flegrei (Pozzuoli), and linkages with volcanic activity

Carbon dioxide flux from the soil is regularly monitored in selected areas of Vesuvio and Solfatara (Campi Flegrei, Pozzuoli) with the twofold aim of i) monitoring spatial and temporal variations of the degassing process and ii) investigating if the surface phenomena could provide information about the processes occurring at depth. At present, the surveyed areas include 15 fixed points around the rim of Vesuvio and 71 fixed points in the floor of Solfatara crater. Soil CO₂ flux has been measured since 1998, at least once a month, in both areas. In addition, two automatic permanent stations, located at Vesuvio and Solfatara, measure the CO₂ flux and some environmental parameters that can potentially influence the CO₂ diffuse degassing. Series acquired by continuous stations are characterized by an annual periodicity that is related to the typical periodicities of some meteorological parameters. Conversely, series of CO₂ flux data arising from periodic measurements over the arrays of Vesuvio and Solfatara are less dependent on external factors such as meteorological parameters, local soil properties (porosity, hydraulic conductivity) and topographic effects (high or low ground). Therefore we argue that the long-term trend of this signal contains the “best” possible representation of the endogenous signal related to the upflow of deep hydrothermal fluids.     

Volcanic CO2 flux measurement at Campi Flegrei by tunable diode laser absorption spectroscopy

Near-infrared room temperature tunable diode lasers (TDL) have recently found increased usage in atmospheric chemistry and air monitoring research, but applications in volcanology are still limited to a few examples. Here, we explored the potential of a commercial infrared laser unit (GasFinder 2.0 from Boreal Laser Ltd) for measurement of volcanic CO₂ mixing ratios, and ultimately for estimating the volcanic CO₂ flux. Our field tests were conducted at Campi Flegrei near Pozzuoli, Southern Italy, where the GasFinder was used during three campaigns in October 2012, January 2013 and May 2013 to repeatedly measure the path-integrated mixing ratios of CO₂ along cross sections of the atmospheric plumes of two major fumarolic fields (Solfatara and Pisciarelli). By using a tomographic post-processing routine, we resolved, for each of the two fields, the contour maps of CO₂ mixing ratios in the atmosphere, from the integration of which (and after multiplication by the plumes’ transport speeds) the CO₂ fluxes were finally obtained. We evaluate a total CO₂ output from the Campi Flegrei fumaroles of ～490 Mg/day, in line with independent estimates based on in situ (Multi-GAS) observations. We conclude that TDL technique may enable CO₂ flux quantification at other volcanoes worldwide.     

The determination of deep temperatures by means of the CO-CO2-H2-H2O geothermometer: an example using fumaroles in the Campi Flegrei,Italy

Chromatographic analyses of fumarolic gases, collected in sampling bottles containing an alkaline solution, have been carried out using a thermal conductivity detector and a flame ionization detector, after catalytic conversion of CO and CH₄. The latter method enables the concentration of carbon monoxide to be measured with sufficient accuracy for use in a CO-CO₂-H₂-H₂O geothermometer. Application of this geothermometer to fumaroles in the crater of Solfatara in the Campi Flegrei, Italy, indicates that they are fed from a steam reservoir at 250±15 °C and at 10^–36±2atm of oxygen. On the other hand, the CH₄-CO₂-H₂-H₂O geothermobarometer seems to re-equilibrate at superficial temperatures and cannot be used for infering thermodynamic conditions at depth. Regular sampling of these fumaroles together with a geothermometric interpretation of the gas analyses provides a means of monitoring, with comparative accuracy, the chemical and thermal evolution of the hydrothermal reservoir below the Solfatara crater. Such monitoring would probably detect an increase in temperature at depth and the injection of magmatic gas into the reservoir.     

Gas exchange between Baikal and the atmosphere during under-ice period

In the under-ice period, gas exchange between Baikal and the atmosphere is taking place through a system of coastal and perennial fractures and airholes in the ice, as well as through the surface of the ice-free part of the lake at the Angara source [24]. The total area of the open water never exceeds 0.03% of lake water area. The emission of CO₂ in the course of ice sublimation over the entire period is ≤0.02 g CO₂ from 1 m². The transport of dissolved gases from under-ice water into the atmosphere is limited by molecular diffusion in microfractions of ice cover. The narrow daily variations of CO₂ in the air in lake coastal zone is due to the effect of populated localities on its coast and large coniferous forests, which serve as diffuse sources of CO₂, as well as diurnal variations of the direction and velocity of air mass transport by local winds.     

CO2 absorption of sandy soil induced by rainfall pulses in a desert ecosystem

Soil CO₂ flux is strongly influenced by precipitation in many ecosystem types, yet knowledge of the effects of precipitation on soil CO₂ flux in semi‐arid desert ecosystems remains insufficient, particularly for sandy soils. To address this, we investigated the response of sandy soil CO₂ flux to rainfall pulses in a desert ecosystem in northern China during August–September 2011. Significant changes (P < 0.05) were found in diel patterns of soil CO₂ flux induced by small (2.1 mm), moderate (12.4 mm) and large (19.7 mm) precipitation events. Further analysis indicated that rainfall pulses modified the response of soil CO₂ flux to soil temperature, including hysteresis between soil CO₂ flux and soil temperature, with F_s higher when T_s was increasing than when T_s was decreasing, and the linear relationship between them. Moreover, our results showed that rainfall could result in absorption of atmospheric CO₂ by soil, possibly owing to mass flow of CO₂ induced by a gradient of gas pressure between atmosphere and soil. After each precipitation event, soil CO₂ flux recovered exponentially to pre‐rainfall levels with time, with the recovery times exhibiting a positive correlation with precipitation amount. On the basis of the amounts of precipitation that occurred at our site during the measurement period (August–September), the accumulated rain‐induced carbon absorption evaluated for rainy days was 1.068 g C m^?2; this corresponds approximately to 0.5–2.1% of the net primary production of a typical desert ecosystem. Thus, our results suggest that rainfall pulses can strongly influence carbon fluxes in desert ecosystems. Copyright © 2014 John Wiley & Sons, Ltd.     

Measurement of Natural Losses of LNAPL Using CO2 Traps

Efflux of CO₂ above releases of petroleum light nonaqueous phase liquids (LNAPLs) has emerged as a critical parameter for resolving natural losses of LNAPLs and managing LNAPL sites. Current approaches for resolving CO₂ efflux include gradient, flux chamber, and mass balance methods. Herein a new method for measuring CO₂ efflux above LNAPL bodies, referred to as CO₂ traps, is introduced. CO₂ traps involve an upper and a lower solid phase sorbent elements that convert CO₂ gas into solid phase carbonates. The sorbent is placed in an open vertical section of 10 cm ID polyvinyl chloride (PVC) pipe located at grade. The lower sorbent element captures CO₂ released from the subsurface via diffusion and advection. The upper sorbent element prevents atmospheric CO₂ from reaching the lower sorbent element. CO₂ traps provide integral measurement of CO₂ efflux based over the period of deployment, typically 2 to 4 weeks. Favorable attributes of CO₂ traps include simplicity, generation of integral (time averaged) measurement, and a simple means of capturing CO₂ for carbon isotope analysis. Results from open and closed laboratory experiments indicate that CO₂ traps quantitatively capture CO₂. Results from the deployment of 23 CO₂ traps at a former refinery indicate natural loss rates of LNAPL (measured in the fall, likely concurrent with high soil temperatures and consequently high degradation rates) ranging from 13,400 to 130,000 liters per hectare per year (L/Ha/year). A set of field triplicates indicates a coefficient of variation of 18% (resulting from local spatial variations and issues with measurement accuracy).     

A method for shipboard measurement of CO2 partial pressure in seawater

A dynamic method suitable for shipboard measurement of the partial pressure of CO₂ exerted by a seawater sample has been developed. The system consists of a paddle-wheel-type gas-water equilibrator and an infrared gas analyzer. Since the system is open to the atmosphere at the in-take and the exhaust ends, it can be operated stably on shipboard conditions. A precision of ±2% has been obtained for shipboard measurement of pCO₂.     

Geothermal energy release at the Solfatara of Pozzuoli (Phlegraean Fields): Phreatic and phreatomagmatic explosion risk implications

The H₂O, CO₂ and H₂S outputs at the Solfatara of Pozzuoli have been measured and a map of the exhaling areas has also been made. The energy released at the surface by the fluids has been estimated to be 10¹⁹ ergs/day.The presence of aquifers at Phlegraean Fields increases the phreatic and phreatomagmatic explosion risk.Our results suggest that even if an uprising magma may interact with water at depth, an explosion could occur only at the shallow levels of a few hundred meters. Since the transfer of energy toward the surface is favoured by the presence of fractures, a detailed analysis of the deep fracture network would help to evaluate the risk levels of the various areas of Phlegraean Fields.     

Modeling hydrothermal fluid circulation and gravity signals at the Phlegraean Fields caldera

The Phlegraean Fields caldera is an active volcanic system where episodes of ground deformation are accompanied by significant changes in geochemical and geophysical parameters monitored at the surface. These changes derive from a complex interaction between magmatic system and hydrothermal fluid circulation. We calculate the gravity changes associated with the variable density of hydrothermal fluids. We simulate the multi-phase and multi-component fluid circulation triggered by a pulsating magma degassing, periodically increasing the discharge of CO₂-enriched fluids into the shallow hydrothermal system. The simulated evolution of the hydrothermal system successfully reproduces the observed composition of gas discharged at the surface. At the same time, results indicate that changes in average fluid density generate a detectable gravity signal that is of the same order of magnitude of the observed changes. This contribution to gravity changes can explain the peculiar behavior of gravity data collected at Solfatara, where surface hydrothermal phenomena are present. Simultaneous fitting of two independent sets of monitoring data (gas composition and gravity changes) confirms the conceptual model proposed for the hydrothermal system at Solfatara, and it provides new insights for the interpretation of gravity data.     

Transfer of carbon dioxide and methane through the soil‐water‐atmosphere system at Mer Bleue peatland,Canada

Surface waters associated with peatlands, supersaturated with CO₂ and CH₄ with respect to the atmosphere, act as important pathways linking a large and potentially unstable global repository of C to the atmosphere. Understanding the drivers and mechanisms which control C release from peatland systems to the atmosphere will contribute to better management and modelling of terrestrial C pools. We used non‐dispersive infra‐red (NDIR) CO₂ sensors to continuously measure gas concentrations in a beaver pond at Mer Bleue peatland (Canada); measurements were made between July and August 2007. Concentrations of CO₂ in the surface water (10 cm) reached 13 mg C l^?1 (epCO₂ 72), and 26 mg C l^?1 (epCO₂ 133) at depth (60 cm). The study also showed large diurnal fluctuations in dissolved CO₂ which ranged in amplitude from ～1·6 mg C l^?1 at 10 cm to ～0·2 mg C l^?1 at 60 cm depth. CH₄ concentration and supersaturation (epCH₄) measured using headspace analysis averaged 1·47 mg C l^?1 and 3252, respectively; diurnal cycling was also evident in CH₄ concentrations. Mean estimated evasion rates of CO₂ and CH₄ over the summer period were 44·92 ± 7·86 and 0·44 ± 0·25 µg C m^?2s^?1, respectively. Open water at Mer Bleue is a significant summer hotspot for greenhouse gas emissions within the catchment. Our results suggest that CO₂ concentrations during the summer in beaver ponds at Mer Bleue are strongly influenced by biological processes within the water column involving aquatic plants and algae (in situ photosynthesis and respiration). In terms of carbon cycling, soil‐stream connectivity at this time of year is therefore relatively weak. Copyright © 2008 John Wiley & Sons, Ltd.     

Seasonal variations in pCO2 and its controlling factors in surface seawater of the northern East China Sea

Surface partial pressure of CO₂ (pCO₂), temperature, salinity, nutrients, and chlorophyll a were measured in the East China Sea (ECS; 31°30′–34°00′N to 124°00′–127°30′E) in August 2003 (summer), May 2004 (spring), October 2004 (early fall), and November 2005 (fall). The warm and saline Tsushima Warm Current was observed in the eastern part of the survey area during four cruises, and relatively low salinity waters due to outflow from the Changjiang (Yangtze River) were observed over the western part of the survey area. Surface pCO₂ ranged from 236 to 445 μatm in spring and summer, and from 326 to 517 μatm in fall. Large pCO₂ (values >400 μatm) occurred in the western part of the study area in spring and fall, and in the eastern part in summer. A positive linear correlation existed between surface pCO₂ and temperature in the eastern part of the study area, where the Tsushima Warm Current dominates; this correlation suggests that temperature is the major factor controlling surface pCO₂ distribution in that area. In the western part of the study area, however, the main controlling factor is different and seasonally complex. There is large transport in this region of Changjiang Diluted Water in summer, causing low salinity and low pCO₂ values. The relationship between surface pCO₂ and water stability suggests that the amount of mixing and/or upwelling of CO₂-rich water might be the important process controlling surface pCO₂ levels during spring and fall in this shallow region. Sea–air CO₂ flux, based on the application of a Wanninkhof [1992. Relationship between wind speed and gas exchange over the ocean. Journal of Geophysical Research 97, 7373–7382] formula for gas transfer velocity and a set of monthly averaged satellite wind data, were −5.04±1.59, −2.52±1.81, 1.71±2.87, and 0.39±0.18 mmol m⁻² d⁻¹ in spring, summer, early fall, and fall, respectively, in the northern ECS. The ocean in this study area is therefore a carbon sink in spring and summer, but a weak source or in equilibrium with the atmosphere in fall. If the winter flux value is assumed to have been the mean of autumnal and vernal values, then the northern ECS absorbs about 0.013 Pg C annually. That result suggests that the northern ECS is a net sink for atmospheric CO₂, a result consistent with previous studies.     

Seasonal change in CO2 and H2O exchange between grassland and atmosphere

The seasonal change in CO₂ flux over an artificial grassland was analyzed from the ecological and meteorological point of view. This grassland contains C₃ and C₄ plants; the three dominant species belonging to the Gramineae; Festuca elatior (C₃) dominated in early spring, and Imperata cylindrica (C₄) and Andropogon virginicus (C₄) grew during early summer and became dominant in mid-summer. CO₂ flux was measured by the gradient method, and the routinely observed data for the surface-heat budget were used to analyze the CO₂ and H₂O exchange between the grassland and atmosphere. From August to October in 1993, CO₂ flux was reduced to around half under the same solar-radiation conditions, while H₂O flux decreased 20% during the same period. The monthly values of water use efficiency, i.e., ratio of CO₂ flux to H₂O flux decreased from 5.8 to 3.3 mg CO₂/g H₂O from August to October, the Bowen ratio increased from 0.20 to 0.30, and the ratio of the bulk latent heat transfer coefficient C_E to the sensible heat transfer coefficient C_H was maintained around 0.40-0.50. The increase in the Bowen ratio was explained by the decrease in air temperature from 22.3 °C in August to 16.6 °C in October without considering biological effects such as stomatal closure on the individual leaves. The nearly constant C_E/C_H ratios suggested that the contribution ratio of canopy resistance to aerodynamic resistance did not change markedly, although the meteorological conditions changed seasonally. The decrease in the water use efficiency, however, suggested that the photosynthetic rate decreased for individual leaves from August to October under the same radiation conditions. Diurnal variations of CO₂ exchange were simulated by the multi-layer canopy model taking into account the differences in the stomatal conductance and photosynthetic pathway between C₃ and C₄ plants. The results suggested that C₄ plants played a major role in the CO₂ exchange in August, the contribution of C₄ plants decreased in September, and daily variations of CO₂ exchange were mainly due to C₃ plants in October. The results also suggested that the decrease in the net canopy CO₂ exchange from August to October was induced partly by the decrease of net photosynthesis on the individual leaves in both C₄ and C₃ plants, which could be due to aging of the leaves.     

A bivariate stochastic Gamma diffusion model: statistical inference and application to the joint modelling of the gross domestic product and CO2 emissions in Spain

This paper examines the use of a bivariate stochastic Gamma diffusion model to represent the co-evolution of the stochastic variables CO₂ emission and gross domestic product (GDP) in Spain. These variables were selected in view of the strong correlation between them. We compare the results obtained to those provided by the Gamma one-dimensional process with exogenous factors, taking CO₂ emission as an endogenous variable and GDP as the exogenous factor. This methodology was applied to a real case, with two dependent variables: firstly, GDP and CO₂ emission from the combustion of fossil fuels (gas, liquid and solid fuels) and cement manufacture in Spain. And secondly, with GDP and CO₂ emission from the consumption and flaring of natural gas in Spain. The joint dynamic evolution of these factors is represented by the proposed model. In addition, a comparison is made with results obtained from fitting the data using the Gamma diffusion process with external factors, in which GDP is the variable containing the external information. This implementation was carried out on the basis of annual observations of the variables over the periods 1986–2008 and 1986–2009, respectively.     

Geochemical survey of Levante Bay,Vulcano Island (Italy), a natural laboratory for the study of ocean acidification

Shallow submarine gas vents in Levante Bay, Vulcano Island (Italy), emit around 3.6t CO₂ per day providing a natural laboratory for the study of biogeochemical processes related to seabed CO₂ leaks and ocean acidification. The main physico-chemical parameters (T, pH and Eh) were measured at more than 70 stations with 40 seawater samples were collected for chemical analyses. The main gas vent area had high concentrations of dissolved hydrothermal gases, low pH and negative redox values all of which returned to normal seawater values at distances of about 400 m from the main vents. Much of the bay around the vents is corrosive to calcium carbonate; the north shore has a gradient in seawater carbonate chemistry that is well suited to studies of the effects of long-term increases in CO₂ levels. This shoreline lacks toxic compounds (such as H₂S) and has a gradient in carbonate saturation states.     

The role of vibrationally excited nitrogen in the ionosphere

Theoretical and experimental aspects of the production, transformation, diffusion and loss of N₂ in the upper atmosphere are considered. The N₂-CO₂ near-resonant system in theD andE regions is taken into account. We describe our understanding of the methods necessary to find the vibrational populations of N₂ and CO₂ (asymmetric mode of CO₂). The calculations of the vibrational temperatures in theD, E, andF regions for the mid-latitude ionosphere and an aurora are presented. The connection between the excited species and the 4.26-m radiation intensities is considered. The models for the rate coefficient of the reaction of O⁺ with N₂ and the electron density decrease resulting from N₂ in the F region are discussed.     

Soil CO2 flux baseline in an urban monogenetic volcanic field: the Auckland Volcanic Field, New Zealand

The Auckland Volcanic Field (AVF) is a dormant monogenetic basaltic field located in Auckland, New Zealand. Though soil gas CO₂ fluxes are routinely used to monitor volcanic regions, there have been no published studies of soil CO₂ flux or soil gas CO₂ concentrations in the AVF to date or many other monogenetic fields worldwide. We measured soil gas CO₂ fluxes and soil gas CO₂ concentrations in 2010 and 2012 in varying settings, seasons, and times of day to establish a baseline soil CO₂ flux and to determine the major sources of and controlling influences on Auckland's soil CO₂ flux. Soil CO₂ flux measurements varied from 0 to 203 g m^?2 day^?1, with an average of 27.1 g m^?2 day^?1. Higher fluxes were attributed to varying land use properties (e.g., landfill). Using a graphical statistical approach, two populations of CO₂ fluxes were identified. Isotope analyses of δ¹³CO₂ confirmed that the source of CO₂ in the AVF is biogenic with no volcanic component. These data may be used to assist with eruption forecasting in the event of precursory activity in the AVF, and highlight the importance of knowing land use history when assessing soil gas CO₂ fluxes in urban environments.     

Les débits de CO2 et de SO2 volcaniques dans l’atmosphère

Volcanic contribution to the atmosphere can be re-evaluated as 5×10⁷ ton/year of CO₂, which is less than recent industrial contribution. Degassing is more abundant from volcanoes where magma convections are significant. Effective degassing occurs before the magma reaches the surface, that is, when the magma is fluid. Volcanic gas in the atmosphere can affect the population or the vegetation around volcanoes.     

Oxygen diffusion rates in quartz exchanged with CO2

Oxygen self diffusion rates were determined in quartz samples exchanged with¹⁸O-enriched CO₂ between 745 and 900°C and various pressures, and the diffusion profiles were measured using an ion microprobe. The activation energy (Q) and preexponential factor (D₀) at P(CO₂) = P(tot) = 100 bar, for diffusion parallel to the c-axis are 159 ( ± 13) kJ/g atom and 2.10 (+0.75/ −0.55) × 10⁻⁸ cm²/s. This rate is approximately 100 times slower than that obtained from hydrothermal experiments and 100 times faster than a previous 1-bar quartz-O₂ exchange experiment. The oxygen diffusion rate measured at 0.6 bar, 888°C, and at 900°C in vacuum is in agreement with the previous 1-bar exchange experiments with¹⁸O₂. The effect of higher CO₂ pressures is small. At 900°C, the diffusion rate exchanged with CO₂ is = 2.35 × 10⁻¹⁵ cm²/s at 100 bar, 2.24 × 10⁻¹⁵ cm²/s at 3.45 kbar and 8.13 × 10⁻¹⁵ cm²/s at 7.2 kbar.There is probably a diffusing species, other than oxygen, that enhances the oxygen diffusion rate in these quartz-CO₂ systems, relative to that occurring at very low pressures or in a vacuum. The effect of this diffusing species, however, is not as strong as that associated with H₂O. Preserved oxygen isotope fractionations between coexisting minerals in a slowly cooled, high-grade metamorphic terrane will vary depending upon whether a water-rich phase was present or not. Closure temperatures will be approximately 100°C higher in rocks where no water-rich phase was present during cooling. The measured fractionations between coexisting minerals in metamorphic rocks may potentially be used as a sensor of water presence during retrogression.     

The fluvial flux of particulate organic matter from the UK: the emission factor of soil erosion

Soil erosion has been identified as a potential global carbon sink since eroded organic matter is replaced at source and eroded material is readily buried. However, this argument has relied on poor estimates of the total fate of in‐transit particulates and could erroneously imply soil erosion could be encouraged to generate carbon stores. These previous estimates have not considered that organic matter can also be released to the atmosphere as a range of greenhouse gases, not only carbon dioxide (CO₂), but also the more powerful greenhouse gases methane (CH₄) and nitrous oxide (N₂O). As soil carbon lost by erosion is only replaced by uptake of CO₂, this could represent a considerable imbalance in greenhouse gas warming potential, even if it is not significant in terms of overall carbon flux. This work therefore considers the flux of particulate organic matter through UK rivers with respect to both carbon fluxes and greenhouse gas emissions. The results show that, although emissions to the atmosphere are dominated by CO₂, there are also considerable fluxes of CH₄ and N₂O. The results suggest that soil erosion is a net source of greenhouse gases with median emission factors of 5.5, 4.4 and 0.3 tonnes CO_2eq/yr for one tonne of fluvial carbon, gross carbon erosion and gross soil erosion, respectively. This study concludes that gross soil erosion would therefore only be a net sink of both carbon and greenhouse gases if all the following criteria are met: the gross soil erosion rate were very low (<91 tonnes/km²/yr); the eroded carbon were completely replaced by new soil organic matter; and if less than half of the gross erosion made it into the stream network. By establishing the emission factor for soil erosion, it becomes possible to properly account for the benefits of good soil management in minimizing losses of greenhouse gases to the atmosphere as a by‐product of soil erosion. Copyright © 2015 John Wiley & Sons, Ltd.     

Atmospheric pressure and CO2 concentration of potential habitable planet HD40307g

HD40307g is the closest potentially habitable planet discovered today orbiting a K2V star and will be a prime target for future TPF-like missions if its existence is confirmed.Although the atmosphere of HD40307g should be denser and contain more CO2 judging from the amount of radiation it receives from its star,it is unknown how dense and how much CO2 the planetary atmosphere should have.Thus more knowledge on its atmosphere is useful.For HD40307g to have Earth-like climate(288 K global mean surface temperature),we obtain the following combination of atmospheric pressure and CO2 mixing ratio:(1)10-bar+3%CO2;(2)5-bar+10%CO2;(3)3-bar+30%CO2.