Geophysical monitoring technology for CO<Subscript>2</Subscript> sequestration

Geophysical techniques play key roles in the measuring, monitoring, and verifying the safety of CO₂ sequestration and in identifying the efficiency of CO₂-enhanced oil recovery. Although geophysical monitoring techniques for CO₂ sequestration have grown out of conventional oil and gas geophysical exploration techniques, it takes a long time to conduct geophysical monitoring, and there are many barriers and challenges. In this paper, with the initial objective of performing CO₂ sequestration, we studied the geophysical tasks associated with evaluating geological storage sites and monitoring CO₂ sequestration. Based on our review of the scope of geophysical monitoring techniques and our experience in domestic and international carbon capture and sequestration projects, we analyzed the inherent difficulties and our experiences in geophysical monitoring techniques, especially, with respect to 4D seismic acquisition, processing, and interpretation.     

Physics and Seismic Modeling for Monitoring CO<Subscript>2</Subscript> Storage

We present a new petro-elastical and numerical-simulation methodology to compute synthetic seismograms for reservoirs subject to CO₂ sequestration. The petro-elastical equations model the seismic properties of reservoir rocks saturated with CO₂, methane, oil and brine. The gas properties are obtained from the van der Waals equation and we take into account the absorption of gas by oil and brine, as a function of the in situ pore pressure and temperature. The dry-rock bulk and shear moduli can be obtained either by calibration from real data or by using rock-physics models based on the Hertz-Mindlin and Hashin-Shtrikman theories. Mesoscopic attenuation due to fluids effects is quantified by using White's model of patchy saturation, and the wet-rock velocities are calculated with Gassmann equations by using an effective fluid modulus to describe the velocities predicted by White's model. The simulations are performed with a poro-viscoelastic modeling code based on Biot's theory, where viscoelasticity is described by generalizing the solid/fluid coupling modulus to a relaxation function. Using the pseudo-spectral method, which allows general material variability, a complete and accurate characterization of the reservoir can be obtained. A simulation, that considers the Utsira sand of the North Sea, illustrates the methodology.     

Soil H<Subscript>2</Subscript> and CO<Subscript>2</Subscript> Surveys at Several Active Faults in Japan

Soil H₂ and CO₂ surveys were carried out along seven active faults and around the aftershock region of the 2000 Tottori-ken Seibu earthquake in Japan. Diffuse CO₂ effluxes were also measured along one fault and around the 2000 aftershock region. The results show highly variable H₂ concentration in space and time and it seems that the maximum H₂ concentration at each active fault correlates with fault activity as exemplified by the time of the latest big earthquakes. Even though observed H₂ concentrations in four faults were markedly lower than those collected previously in the latter half of the 1970s, it is evident that the higher H₂ concentrations in this study are due to the addition of the fault gases. Comparing the chemical composition of trapped gases (H₂: 5–20% and CO₂/H₂: 0.5–12) in fractured rocks of drill cores bored at the Nojima fault, a soil gas sample with the highest H₂ concentration showed large amounts of the trapped fault gas, diluted with atmospheric component. The profile experiment across a fracture zone at the Yamasaki fault showed higher H₂ concentrations and lower CO₂/H₂ ratios as was observed in soil gas from the fracture zone. A few days after the 2000 Tottori-kei Seibu earthquake, no CO₂ effluxes related to the occurrence of earthquakes were observed at the aftershock region. However, only above the epicenter zone, relatively high H₂ concentrations in soil gases were observed.     

Diffuse CO<Subscript>2</Subscript> degassing at Vesuvio,Italy

At Vesuvio, a significant fraction of the rising hydrothermal–volcanic fluids is subjected to a condensation and separation process producing a CO₂–rich gas phase, mainly expulsed through soil diffuse degassing from well defined areas called diffuse degassing structures (DDS), and a liquid phase that flows towards the outer part of the volcanic cone. A large amount of thermal energy is associated with the steam condensation process and subsequent cooling of the liquid phase. The total amount of volcanic–hydrothermal CO₂ discharged through diffuse degassing has been computed through a sequential Gaussian simulation (sGs) approach based on several hundred accumulation chamber measurements and, at the time of the survey, amounted to 151 t d^–1. The steam associated with the CO₂ output, computed assuming that the original H₂O/CO₂ ratio of hydrothermal fluids is preserved in fumarolic effluents, is 553 t d^–1, and the energy produced by the steam condensation and cooling of the liquid phase is 1.47×10¹² J d^–1 (17 MW). The location of the CO₂ and temperature anomalies show that most of the gas is discharged from the inner part of the crater and suggests that crater morphology and local stratigraphy exert strong control on CO₂ degassing and subsurface steam condensation. The amounts of gas and energy released by Vesuvio are comparable to those released by other volcanic degassing areas of the world and their estimates, through periodic surveys of soil CO₂ flux, can constitute a useful tool to monitor volcanic activity.Editorial responsibility: H. Shinohara     

Time-dependent CO<Subscript>2</Subscript> variations in Lake Albano associated with seismic activity

Lake Albano (Alban Hills volcanic complex, Central Italy) is located in a densely populated area near Rome. The deep lake waters have significant dissolved CO₂ concentrations, probably related to sub-lacustrine fluid discharges fed by a pressurized CO₂-rich reservoir. The analytical results of geochemical surveys carried out in 1989–2010 highlight the episodes of CO₂ removal from the lake. The total mass of dissolved CO₂ decreased from ∼5.8 × 10⁷ kg in 1989 to ∼0.5 × 10⁷ kg in 2010, following an exponential decreasing trend. Calculated values of both dissolved inorganic carbon and CO₂ concentrations along the vertical profile of the lake indicate that this decrease is caused by CO₂ release from the epilimnion, at depth <9 m, combined with (1) water circulation at depth <95 m and (2) CO₂ diffusion from the deeper lake layers. According to this model, Lake Albano was affected by a large CO₂ input that coincided with the last important seismic swarm at Alban Hills in 1989, suggesting an intimate relationship between the addition of deep-originated CO₂ to the lake and seismic activity. In the case of a CO₂ degassing event of an order of magnitude larger than the one that occurred in 1989, the deepest part of Lake Albano would become CO₂-saturated, resulting in conditions compatible with the occurrence of a gas outburst. These results reinforce the idea that a sudden CO₂ input into the lake may cause the release of a dense gas cloud, presently representing the major volcanic threat for this densely populated area.     

Uncertainty analysis of CO<Subscript>2</Subscript> flux components in subtropical evergreen coniferous plantation

We present an uncertainty analysis of ecological process parameters and CO₂ flux components (R _eco, NEE and gross ecosystem exchange (GEE)) derived from 3 years’ continuous eddy covariance measurements of CO₂ fluxes at subtropical evergreen coniferous plantation, Qianyanzhou of ChinaFlux. Daily-differencing approach was used to analyze the random error of CO₂ fluxes measurements and bootstrapping method was used to quantify the uncertainties of three CO₂ flux components. In addition, we evaluated different models and optimization methods in influencing estimation of key parameters and CO₂ flux components. The results show that: (1) Random flux error more closely follows a double-exponential (Laplace), rather than a normal (Gaussian) distribution. (2) Different optimization methods result in different estimates of model parameters. Uncertainties of parameters estimated by the maximum likelihood estimation (MLE) are lower than those derived from ordinary least square method (OLS). (3) The differences between simulated R_eco, NEE and GEE derived from MLE and those derived from OLS are 12.18% (176 g C·m⁻²·a⁻¹), 34.33% (79 g C·m⁻²·a⁻¹) and 5.4% (92 g C·m⁻²·a⁻¹). However, for a given parameter optimization method, a temperature-dependent model (T_model) and the models derived from a temperature and water-dependent model (TW_model) are 1.31% (17.8 g C·m⁻²·a⁻¹), 2.1% (5.7 g C·m⁻²·a⁻¹), and 0.26% (4.3 g C·m⁻²·a⁻¹), respectively, which suggested that the optimization methods are more important than the ecological models in influencing uncertainty in estimated carbon fluxes. (4) The relative uncertainty of CO₂ flux derived from OLS is higher than that from MLE, and the uncertainty is related to timescale, that is, the larger the timescale, the smaller the uncertainty. The relative uncertainties of R_eco, NEE and GEE are 4%−8%, 7%−22% and 2%−4% respectively at annual timescale. Supported by the National Natural Science Foundation of China (Grant No. 30570347), Innovative Research International Partnership Project of the Chinese Academy of Sciences (Grant No. CXTD-Z2005-1) and National Basic Research Program of China (Grant No. 2002CB412502)     

Structure and CO<Subscript>2</Subscript> budget of Merapi volcano during inter-eruptive periods

Soil temperature and gas (CO₂ concentration and flux) have been investigated at Merapi volcano (Indonesia) during two inter-eruptive periods (2002 and 2007). Precise imaging of the summit crater and the spatial pattern of diffuse degassing along a gas traverse on the southern slope are interpreted in terms of summit structure and major caldera organization. The summit area is characterized by decreasing CO₂ concentrations with distance from the 1932 crater rim, down to atmospheric levels at the base of the terminal cone. Similar patterns are measured on any transect down the slopes of the cone. The spatial distribution of soil gas anomalies suggests that soil degassing is controlled by structures identified as concentric historical caldera rims (1932, 1872, and 1768), which have undergone severe hydrothermal self-sealing processes that dramatically lower the permeability and porosity of soils. Temperature and CO₂ flux measurements in soils near the dome display heterogeneous distributions which are consistent with a fracture network identified by previous geophysical studies. These data support the idea that the summit is made of isolated and mobile blocks, whose boundaries are either sealed by depositional processes or used as pathways for significant soil degassing. Within this context, self-sealing both prevents long-distance soil degassing and controls heat and volatile transfers near the dome. A rough estimate of the CO₂ output through soils near the dome is 200–230 t day⁻¹, i.e. 50% of the estimated total gas output from the volcano summit during these quiescent periods. On Merapi’s southern slope, a 2,500 m long CO₂ traverse shows low-amplitude anomalies that fit well with a recently observed electromagnetic anomaly, consistent with a faulted structure related to an ancient avalanche caldera rim. Sub-surface soil permeability is the key parameter that controls the transfer of heat and volatiles within the volcano, allowing its major tectonic architecture to be revealed by soil gas and soil temperature surveys.     

Links between global CO<Subscript>2</Subscript> variability and climate anomalies of biomes

The global rate of fossil fuel combustion continues to rise, but the amount of CO₂ accumulating in the atmosphere has not increased accordingly. The causes for this discrepancy are widely debated. Particularly, the location and drivers for the interannual variability of atmospheric CO₂ are highly uncertain. Here we examine links between global atmospheric CO₂ growth rate (CGR) and the climate anomalies of biomes based on (1986–1995) global climate data of ten years and accompanying satellite data sets. Our results show that four biomes, the tropical rainforest, tropical savanna, C₄ grassland and boreal forest, and their responses to climate anomalies, are the major climate-sensitive CO₂ sinks/sources that control the CGR. The nature and magnitude by which these biomes respond to climate anomalies are generally not the same. However, one common influence did emerge from our analysis; the extremely high CGR observed for the one extreme El Niño year was caused by the response of the tropical biomes (rainforest, savanna and C₄ grassland) to temperature.     

Seasonal dynamics of CO<Subscript>2</Subscript> fluxes from subtropical plantation coniferous ecosystem

As one component of ChinaFLUX, the measurement of CO₂ flux using eddy covariance over subtropical planted coniferous ecosystem in Qianyanzhou was conducted for a long term. This paper discusses the seasonal dynamics of net ecosystem exchange (NEE), ecosystem respiration (RE) and gross ecosystem exchange (GEE) between the coniferous ecosystem and atmosphere along 2003 and 2004. The variations of NEE, RE and GEE show obvious seasonal variabilities and correlate to each other, i.e. lower in winter and drought season, but higher in summer; light, temperature and soil water content are the main factors determining NEE; air temperature and water vapor pressure deficit (VPD) influence NEE with stronger influence from VPD. Under the proper light condition, drought stress could decrease the temperature range for carbon capture in planted coniferous, air temperature and precipitation controlled RE; The NEE, RE, and GEE for planted coniferous in Qianyanzhou are ?387.2 g C·m^?2 a^?1, 1223.3 g C·m^?2 a^?1, ?1610.4 g C·m^?2 a^?1 in 2003 and ?423.8 g C·m^?2 a^?1, 1442.0 g C·m^?2 a^?1, ?1865.8 g C·m^?2 a^?1 in 2004, respectively, which suggest the intensive ability of plantation coniferous forest on carbon absorbing in Qianyanzhou.     

Shear wave velocity prediction during CO<Subscript>2</Subscript>-EOR and sequestration in the Gao89 well block of the Shengli Oilfield

Shear-wave velocity is a key parameter for calibrating monitoring time-lapse 4D seismic data during CO₂-EOR (Enhanced Oil Recovery) and CO₂ sequestration. However, actual S-wave velocity data are lacking, especially in 4D data for CO₂ sequestration because wells are closed after the CO₂ injection and seismic monitoring is continued but no well log data are acquired. When CO₂ is injected into a reservoir, the pressure and saturation of the reservoirs change as well as the elastic parameters of the reservoir rocks. We propose a method to predict the S-wave velocity in reservoirs at different pressures and porosities based on the Hertz–Mindlin and Gassmann equations. Because the coordination number is unknown in the Hertz–Mindlin equation, we propose a new method to predict it. Thus, we use data at different CO₂ injection stages in the Gao89 well block, Shengli Oilfield. First, the sand and mud beds are separated based on the structural characteristics of the thin sand beds and then the S-wave velocity as a function of reservoir pressure and porosity is calculated. Finally, synthetic seismic seismograms are generated based on the predicted P- and S-wave velocities at different stages of CO₂ injection.     

First <Superscript>13</Superscript>C/<Superscript>12</Superscript>C isotopic characterisation of volcanic plume CO<Subscript>2</Subscript>

We describe analytical details and uncertainty evaluation of a simple technique for the measurement of the carbon isotopic composition of CO₂ in volcanic plumes. Data collected at Solfatara and Vulcano, where plumes are fed by fumaroles which are accessible for direct sampling, were first used to validate the technique. For both volcanoes, the plume-derived carbon isotopic compositions are in good agreement with the fumarolic compositions, thus providing confidence on the method, and allowing its application at volcanoes where the volcanic component is inaccessible to direct sampling. As a notable example, we applied the same method to Mount Etna where we derived a δ¹³C of volcanic CO₂ between −0.9 ± 0.27‰ and −1.41 ± 0.27‰ (Bocca Nuova and Voragine craters). The comparison of our measurements to data reported in previous work highlights a temporal trend of systematic increase of δ¹³C values of Etna CO₂ from ~ −4‰, in the 1970’s and the 1980’s, to ~ −1‰ at the present time (2009). This shift toward more positive δ¹³C values matches a concurrent change in magma composition and an increase in the eruption frequency and energy. We discuss such variations in terms of two possible processes: magma carbonate assimilation and carbon isotopic fractionation due to magma degassing along the Etna plumbing system. Finally, our results highlight potential of systematic measurements of the carbon isotopic composition of the CO₂ emitted by volcanic plumes for a better understanding of volcanic processes and for improved surveillance of volcanic activity.     

Study on the processing method of nighttime CO<Subscript>2</Subscript> eddy covariance flux data in ChinaFLUX

At present, using Eddy Covariance (EC) method to estimate the “true value” of carbon sequestration in terrestrial ecosystem arrests more attention. However, one issue is how to solve the uncertainty of observations (especially the nighttime CO₂ flux data) appearing in post-processing CO₂ flux data. The ratio of effective and reliable nighttime EC CO₂ flux data to all nighttime data is relatively low (commonly, less than 50%) for all the long-term and continuous observation stations in the world. Thus, the processing method of nighttime CO₂ flux data and its effect analysis on estimating CO₂ flux annual sums are very important. In this paper, the authors analyze and discuss the reasons for underestimating nighttime CO₂ flux using EC method, and introduce the general theory and method for processing nighttime CO₂ flux data. By analyzing the relationship between nighttime CO₂ flux and air fraction velocity u*, we present an alternate method, Average Values Test (AVT), to determine the thresholds of fraction velocity (u*_c) for screening the effective nighttime CO₂ flux data. Meanwhile, taking the data observed in Yucheng and Changbai Mountains stations for an example, we analyze and discuss the effects of different methods or parameters on nighttime CO₂ flux estimations. Finally, based on the data of part ChinaFLUX stations and related literatures, empirical models of nighttime respiration at different sites in ChinaFLUX are summarized.     

An improved constraint method in optimal estimation of CO<Subscript>2</Subscript> from GOSAT SWIR observations

We propose an algorithm that combines a pre-processing step applied to the a priori state vector prior to retrievals, with the modified damped Newton method (MDNM), to improve convergence. The initial constraint vector pre-processing step updates the initial state vector prior to the retrievals if the algorithm detects that the initial state vector is far from the true state vector in extreme cases where there are CO₂ emissions. The MDNM uses the Levenberg-Marquardt parameter γ, which ensures a positive Hessian matrix, and a scale factor α, which adjusts the step size to optimize the stability of the convergence. While the algorithm iteratively searches for an optimized solution using observed spectral radiances, MDNM adjusts parameters γ and α to achieve stable convergence. We present simulated retrieval samples to evaluate the performance of our algorithm and comparing it to existing methods. The standard deviation of our retrievals adding random noise was less than 3.8 ppmv. After pre-processing the initial estimate when it was far from the true value, the CO₂ retrieval errors in the boundary layers were within 1.2 ppmv. We tested the MDNM algorithm’s performance using GOSAT L1b data with cloud screening. Our preliminary validations comparing the results to TCCON FTS measurements showed that the average bias was less than 1.8 ppm and the correlation coefficient was approximately 0.88, which was larger than for the GOSAT L2 product.     

Soil organic carbon storage and soil CO<Subscript>2</Subscript> flux in the alpine meadow ecosystem

High-resolution sampling, measurements of organic carbon contents and ¹⁴C signatures of selected four soil profiles in the Haibei Station situated on the northeast Tibetan Plateau, and application of ¹⁴C tracing technology were conducted in an attempt to investigate the turnover times of soil organic carbon and the soil-CO₂ flux in the alpine meadow ecosystem. The results show that the organic carbon stored in the soils varies from 22.12×10⁴ kg C hm⁻² to 30.75×10⁴ kg C hm⁻² in the alpine meadow ecosystems, with an average of 26.86×10⁴ kg C hm⁻². Turnover times of organic carbon pools increase with depth from 45 a to 73 a in the surface soil horizon to hundreds of years or millennia or even longer at the deep soil horizons in the alpine meadow ecosystems. The soil-CO₂ flux ranges from 103.24 g C m⁻² a⁻¹ to 254.93 gC m⁻² a⁻¹, with an average of 191.23 g C m⁻² a⁻¹. The CO₂ efflux produced from microbial decomposition of organic matter varies from 73.3 g C m⁻² a⁻¹ to 181 g C m⁻² a⁻¹. More than 30% of total soil organic carbon resides in the active carbon pool and 72.8%281.23% of total CO₂ emitted from organic matter decomposition results from the topsoil horizon (from 0 cm to 10 cm) for the Kobresia meadow. Responding to global warming, the storage, volume of flow and fate of the soil organic carbon in the alpine meadow ecosystem of the Tibetan Plateau will be changed, which needs further research. Supported by the National Natural Science Foundation of China (Grant Nos. 40231015, 40471120 and 40473002) and the Guangdong Provincial Natural Science Foundation of China (Grant No. 06300102)     

The characteristics of atmospheric CO<Subscript>2</Subscript> concentration variation of four national background stations in China

Atmospheric carbon dioxide is an important kind of greenhouse gas which influences global temperature. Its concentration variation could indicate the distribution of human and natural activities in various regions. Through the non-dispersive infrared method, flask sampling of atmospheric CO₂ concentration was measured weekly at four national background stations including Waliguan, Shangdianzi, Lin’an, and Longfengshan. Based on the data collected from September 2006 to August 2007, along with the Waliguan station’s experience on in situ observational data processing, the selection methods for sampling data through the atmospheric background CO₂ concentration analysis were preliminarily discussed. On the basis of this result, the variation features of the four typical regions’ atmospheric background CO₂ concentration was analyzed for the first time. The results show that the atmospheric CO₂ concentration at Waliguan, Shangdianzi, Lin’an, and Longfengshan is 383.5, 385.9, 387.8, and 384.3 ppm, respectively. During the research period, CO₂ concentration at the Waliguan station changed slightly. However, the CO₂ concentration changed sharply at the Shangdianzi and the Lin’an stations due to the great influence of human activities in the Jingjinji and the Changjiang Delta economic zones, and changed regularly with seasons at Longfengshan station under dual influences of human activities and plant photosynthesis. The results from this study can lay the foundation for more profound studies on atmospheric CO₂ concentration level of different areas in China, and could be used to improve the understanding of carbon source and sink distribution.     

Carbon assimilation characteristics of plants in oasis-desert ecotone and their response to CO<Subscript>2</Subscript> enrichment

Six species of more than 20-year-old desert woody plants in the oasis-desert ecotone were selected for study. The results showed that: (1) in different growing seasons δ¹³C values of assimilating organ varied between -14%. and -16%. for Haloxylon ammodendron (HA),-14%. - -15%. for Calligonum mongolicum (CM) and -25%. - -28%. for Caragana korshinskii (CK), Nitraria sphaerocarpa (NS) and Hedysarum scoparium (HS). (2) The net photosynthetic rate (Pn) of HA and CM was significantly higher than those of the other species. With the decrease in Pn for the six species, their intercellular CO₂ concentration increased, but stomatal limitation value decreased under the intensive light. At the same time, the photochemical efficiency of PS II dropped to different degrees. (3) The CO₂ enrichment experiment demonstrated that, Pn of HA and CM increased to different extent under 450 μmol/mol, but their Pn reduced or approximated to the current condition under 650 μmol/mol. Under 450 μmol/mol the efficiency for solar energy utilization of CK and HS significantly reduced and under 650 μmol/mol their respiration rate exceeded photosynthesis rate. It can be concluded that HA and CM have some function of pathway for C₄ but the other three species have the function for C₃. The decline in their Pn is mainly caused by non-stomatal factors. HA, CM, CK and HS exhibited photoinhibition, which disappeared in a short time. This is a kind of positive readjustment to adapting to the desert environment. HA and CM can adapt to the high CO₂ environment, but CK and HS cannot. With the rise in atmospheric CO₂ concentration and climate warming, the latter two species in the oasis-desert ecotone may be gradually degraded or even disappear.     

Seasonal and annual variation of CO<Subscript>2</Subscript> flux above a broad-leaved Korean pine mixed forest

Long-term measurement of carbon metabolism of old-growth forests is critical to predict their behaviors and to reduce the uncertainties of carbon accounting under changing climate. Eddy covariance technology was applied to investigate the long-term carbon exchange over a 200 year-old Chinese broad-leaved Korean pine mixed forest in the Changbai Mountains (128°28′E and 42°24′N, Jilin Province, P. R. China) since August 2002. On the data obtained with open-path eddy covariance system and CO₂ profile measurement system from Jan. 2003 to Dec. 2004, this paper reports (i) annual and seasonal variation of F _NEE, F _GPP and R _E; (ii) regulation of environmental factors on phase and amplitude of ecosystem CO₂ uptake and release Corrections due to storage and friction velocity were applied to the eddy carbon flux.L_AI and soil temperature determined the seasonal and annual dynamics of F_GPP and R_E separately. V_PD and air temperature regulated ecosystem photosynthesis at finer scales in growing seasons. Water condition at the root zone exerted a significant influence on ecosystem maintenance carbon metabolism of this forest in winter.The forest was a net sink of atmospheric CO₂ and sequestered ?449 g C·m^?2 during the study period; ?278 and ?171 gC·m^?2 for 2003 and 2004 respectively. F _GPP and F _RE over 2003 and 2004 were ?1332, ?1294 g C·m^?2. and 1054, 1124 g C·m^?2 respectively. This study shows that old-growth forest can be a strong net carbon sink of atmospheric CO₂.There was significant seasonal and annual variation in carbon metabolism. In winter, there was weak photosynthesis while the ecosystem emitted CO₂. Carbon exchanges were active in spring and fall but contributed little to carbon sequestration on an annual scale. The summer is the most significant season as far as ecosystem carbon balance is concerned. The 90 days of summer contributed 66.9, 68.9% of F _GPP, and 60.4, 62.1% of R _E of the entire year.     

Geochemical evidence of the renewal of volcanic activity inferred from CO<Subscript>2</Subscript> soil and SO<Subscript>2</Subscript> plume fluxes: the 2007 Stromboli eruption (Italy)

On 27 February 2007, a new eruption occurred on Stromboli which lasted until 2 April. It was characterized by effusive activity on the Sciara del Fuoco and by a paroxysmal event (15 March). This crisis represented an opportunity for us to refine the model that had been developed previously (2002–2003 eruption) and to improve our understanding of the relationship between the magmatic dynamics of the volcano and the geochemical variations in the fluids. In particular, the evaluation of the dynamic equilibrium between the volatiles (CO₂ and SO₂) released from the magma and the corresponding fluids discharged from the summit area allowed us to evaluate the level of criticality of the volcanic activity. One of the major accomplishments of this study is a 4-year database of summit soil CO₂ flux on the basis of which we define the thresholds (low–medium–high) for this parameter that are empirically based on the natural volcanological evolution of Stromboli. The SO₂ fluxes of the degassing plume and the CO₂ fluxes emitted from the soil at Pizzo Sopra la Fossa are also presented. It is noteworthy that geochemical signals of volcanic unrest have been clearly identified before, during and after the effusive activity. These signals were found almost simultaneously in the degassing plume (SO₂ flux) and in soil degassing (CO₂ flux) at the summit, although the two degassing processes are shown to be clearly different. The interpretation of the results will be useful for future volcanic surveillance at Stromboli.     

The crystal structure of (Fe<Subscript>4</Subscript>Cr<Subscript>4</Subscript>Ni)<Subscript>9</Subscript>C<Subscript>4</Subscript>

(Fe4Cr4Ni)9C4 is a metal carbide mineral formed by combination of Fe, Cr and Ni with C. It occurs in a chromite deposit in the Luobusha ophiolite, Tibet. Based on the determination of its crystal structure, the empirical formula is (Fe4.12Cr3.84Ni0.96)8.92C3.70 and the simplified formula is (Fe4Cr4Ni)4C9. The mineral is hexagonal with a = 1.38392(2) nm, c = 0.44690(9) nm, pace group P63 m c, Z=6 and the calculated specific gravity Dx = 7.089 g/cm3. Fe, Cr and Ni occupy different crystallographic sites and their coordination numbers are approximately 12, forming an alternate stacking sequence of flat and puckered layers along the c axis. Some metallic atoms have a defect structure. The interatomic distances of Fe, Cr and Ni are 0.2525-0.2666 nm, and the distances between Fe, Cr, Ni and C are 0.1893-0.2169 nm. The coordination number of carbon is 6. It occurs in interstices of the metallic atoms Fe, Cr and Ni to form trigonalprismatically coordinated polyhedra. These coordination polyhedra are linked with each other via shared corners or shared edges into a new type of metal carbide structure.     

CO<Subscript>2</Subscript> flux evaluation over the evergreen coniferous and broad-leaved mixed forest in Dinghushan,China

The Dinghushan flux observation site, as one of the four forest sites of ChinaFLUX, aims to acquire long-term measurements of CO₂ flux over a typical southern subtropical evergreen coniferous and broad-leaved mixed forest ecosystem using the open path eddy covariance method. Based on two years of data from 2003 to 2004, the characteristics of temporal variation in CO₂ flux and its response to environmental factors in the forest ecosystem are analyzed. Provided two-dimensional coordinate rotation, WPL correction and quality control, poor energy-balance and underestimation of ecosystem respiration during nighttime implied that there could be a CO₂ leak during the nighttime at the site. Using daytime (PAR > 1.0 μmol^?1·m^?2·s^?1) flux data during windy conditions (u* > 0.2 m·s^?1), monthly ecosystem respiration (Reco) was derived through the Michaelis-Menten equation modeling the relationship between net ecosystem C0₂ exchange (NEE) and photosynthetically active radiation (PAR). Exponential function was employed to describe the relationship between Reco and soil temperature at 5 cm depth (Ts05), then Reco of both daytime and nighttime was calculated respectively by the function. The major results are: (i) Derived from the Michaelis-Menten equation, the apparent quantum yield (α) was 0.0027±0.0011 mgCO₂·μmol^?1 photons, and the maximum photosynthetic assimilation rate (Amax) was 1.102±0.288 mgCO₂·m^?2·s^?1. Indistinctive seasonal variation of α or Amax was consistent with weak seasonal dynamics of leaf area index (LAf) in such a lower subtropical evergreen mixed forest, (ii) Monthly accumulated Reco was estimated as 95.3±21.1 gC·m^?2mon^?1, accounting for about 68% of the gross primary product (GPP). Monthly accumulated WEE was estimated as ?43.2±29.6 gC·m^?2·mon^?1. The forest ecosystem acted as carbon sink all year round without any seasonal carbon efflux period. Annual NEE of 2003 and 2004 was estimated as ?563.0 and ?441.2 gC·m^?2·a^?1 respectively, accounting for about 32% of GPP.