Gas composition, concentration and stable isotope ratios (Table 2, 3, 4)

The deployment of CCS (carbon capture and storage) at industrial scale implies the development of effective monitoring tools. Noble gases are tracers usually proposed to track CO2. This methodology, combined with the geochemistry of carbon isotopes, has been tested on available analogues. At first, gases from natural analogues were sampled in the Colorado Plateau and in the French carbogaseous provinces, in both well-confined and leaking-sites. Second, we performed a 2-years tracing experience on an underground natural gas storage, sampling gas each month during injection and withdrawal periods. In natural analogues, the geochemical fingerprints are dependent on the containment criterion and on the geological context, giving tools to detect a leakage of deep-CO2 toward surface. This study also provides information on the origin of CO2, as well as residence time of fluids within the crust and clues on the physico-chemical processes occurring during the geological story. The study on the industrial analogue demonstrates the feasibility of using noble gases as tracers of CO2. Withdrawn gases follow geochemical trends coherent with mixing processes between injected gas end-members. Physico-chemical processes revealed by the tracing occur at transient state. These two complementary studies proved the interest of geochemical monitoring to survey the CO2 behaviour, and gave information on its use.

Sm-Nd, Rb-Sr, and He isotopic composition and hydrocarbon gases in rocks and minerals from the Markov Deep, Mid-Atlantic Ridge rift valley

The paper presents characteristics of the Nd and Sr isotopic systems of ultrabasic rocks, gabbroids, plagiogranites, and their minerals as well as data on helium and hydrocarbons in fluid inclusions of the same samples. Materials presented in this publication were obtained by studying samples dredged from the MAR crest zone at 5°-6°N (U/Pb zircon dating, geochemical and petrological-mineralogical studies). It was demonstrated that variations in the isotopic composition of He entrapped in rocks and minerals were controlled by variable degrees of mixing of juvenile He, which is typical of basaltic glass for MAR (DM source), and atmospheric He. Increase in the atmospheric He fraction in plutonic rocks and, to a lesser degree, in their minerals reflects involvement of seawater or hydrated material of the oceanic crust in magmatic and postmagmatic processes. This conclusion finds further support in positive correlation between the fraction of mantle He (R ratio) and 87Sr/86Sr ratio. High-temperature hydration of ultrabasic rocks (amphibolization) was associated with increase in the fraction of mantle He, while their low-temperature hydration (serpentinization) was accompanied by drastic decrease in this fraction and significant increase in 87Sr/86Sr ratio. Insignificant variations in 143Nd/144Nd (close to 0.5130) and 87Sr/86Sr (0.7035) in most of gabbroids and plagiogranites as well as the fraction of mantle He in these rocks, amphibolites, and their ore minerals indicate that the melts were derived from the depleted mantle. Similar e-Nd values of gabbroids, plagiogranites, and fresh harzburgites (6.77-8.39) suggest that these rocks were genetically related to a single mantle source. e-Nd value of serpentinized lherzolites (2.62) likely reflects relations of these relatively weakly depleted mantle residues to another source. Aforementioned characteristics of the rocks generally reflect various degrees of mixing of depleted mantle components with crustal components (seawater) during metamorphic and hydrothermal processes that accompanied formation of the oceanic crust.

Main components and isotopic composition of gases from mineral waters of the Taman Peninsula and Caucasus

Helium isotope composition as an indicator of the mantle-derived component was studied in gases from mineral springs, stratal waters, and mud volcanoes developed west of the Teberda River valley (10 objects) and two springs in the central segment of the Greater Caucasus orogen between the active El'brus and Kazbek volcanoes. In the western segment of the orogen ratios of 3He/4He = R_corr vary from 46x10**-8 to 114x10**-8 (from 0.33 to 0.81 R_atm, where R_atm = 1.4x10**-6 is the atmospheric ratio). They are substantially lower relative to ratios in the vicinity of El'brus and Kazbek and close to those in samples from the central segment (from 70x10**-8 to 134x10**-8 (from 0.50 to 0.96 R_atm), as well as to ratios previously recorded in the Caucasian Mineral Waters (CMW) area. Moreover, concentration of 3He in them is notably higher than its crustal radiogenic level characteristic of mud volcanoes in the Taman Peninsula, where 3He/4He varies from 1.4x10**-8 to 2.8x10**-8 (from 0.01 to 0.02 R_atm). Nitrogen-methane gas from northern piedmonts of the western Caucasus also contains nonatmogenic components including radiogenic 40Ar (40Ar/36Ar = 900), excessive nitrogen (~87% of total N2 concentration in sample) and mantle He. These data specify distribution of mantle derivates along the orogen strike and age of intrusive magmatic activity in its different segments.

Isotopic-geochemical features of spontaneous gases from mud volcanoes in Eastern Georgia

Isotopic-geochemical study revealed presence of mantle He (3He/4He up to 223x10**-8) in gases from mud volcanoes of Eastern Georgia. This fact confirms that the Middle Kura basin fill encloses an intrusive body previously distinguished from geophysical data. Wide variations of carbon isotopic composition d13C in CH4 and CO2 and chemical composition of gas and water at temporally constant 3He/4He ratio indicate their relation with crustal processes. Unusual direct correlations of 3He/4He ratio with concentrations of He and CH4 and 40Ar/36Ar ratio can be explained by generation of gas in the Cenozoic sequence of the Middle Kura basin.

isotopic composition of gases and interstitial fluides of ODP Site 104-644

Pleistocene- to middle Miocene-age sediment was drilled at Site 341 (67? 20.1'N, 6? 06.6'E) on the inner Voring Plateau during Leg 38 of the Deep Sea Drilling Project (DSDP). In 1985, the Ocean Drilling Program (ODP) returned to the inner Wring Plateau near Site 341 and drilled a new hole at Site 644 (66° 40.7'N, 4° 34.6'E) as part of a transect to study Norwegian Sea paleoenvironments. In Hole 341, gas expansion pockets formed in cores which were recovered from depths below 50 m. This gas was characterized as predominantly methane with delta13C values in the range of -87 to -77 per mil (Morris, 1976, doi:10.2973/dsdp.proc.38.124.1976). At Site 644, sediment gas and pore-water samples were obtained to study the geochemistry of methanogenesis. Of particular interest is the possibility that methane hydrate might be present in these sediments.

Isotopic analysis of core gases at DSDP Leg 84 Holes

Methane carbon-isotopic compositions (d13C values relative to the PDB standard) at Sites 565, 566, 567, and 569 were lighter (enriched in 12C) than -60 per mil, indicating a biogenic origin. In the deeper sections at Sites 568 and 570, d13C values were heavier, approaching -40 per mil, and therefore suggest a thermogenic source. A significant thermogenic source was discounted, however, because the carbon dioxide d13C values in these sections were also anomalously heavy, suggesting that the methane may have formed biogenically by reduction of the heavy carbon dioxide. d13C values of ethane and higher hydrocarbons were measured in several sections from Sites 566 and 570 that contained sufficient C2-C4 hydrocarbon concentrations. Ethane values in six sections (245-395 m sub-bottom) from Site 570 were fairly uniform, ranging from -24 to -26 per mil. These values are among the heaviest ethane values reported for natural gases. The isobutane/ n-butane and isopentane/n-pentane ratios of the core gases suggested that the C2-C5 hydrocarbons are thermally produced by low-temperature chemical diagenesis of indigenous organic matter. This process apparently generates isotopically heavy C2-C5 hydrocarbons. High gas concentrations in the serpentinite basement rocks at Sites 566 and 570 appear to have resulted from migrated biogenic methane gas containing small amounts of immature C2-C5 hydrocarbons.

Noble gases sampled from three cruises in the eastern tropical Atlantic in September 2005 and June/July 2006

Upwelling velocities w in the equatorial band are too small to be directly observed. Here, we apply a recently proposed indirect method, using the observed helium isotope (3He or 4He) disequilibria in the mixed layer. The helium data were sampled from three cruises in the eastern tropical Atlantic in September 2005 and June/July 2006. A one-dimensional two-box model was applied, where the helium air-sea gas exchange is balanced by upwelling from 3He-rich water below the mixed layer and by vertical mixing. The mixing coefficients Kv were estimated from microstructure measurements, and on two of the cruises, Kv exceeded 1 x 10**-4 m**2/s, making the vertical mixing term of the same order of magnitude as the gas exchange and the upwelling term. In total, helium disequilibrium was observed on 54 stations. Of the calculated upwelling velocities, 48% were smaller than 1.0 x 10**-5 m/s, 19% were between 1.0 and 2.0 x 10**-5 m/s, 22% were between 2.0 and 4.0 x 10**-5 m/s, and on 11% of upwelling velocities exceeded this limit. The highest upwelling velocities were found in late June 2006. Meridional upwelling distribution indicated an equatorial asymmetry with higher vertical velocities between the equator and 1° to 2° south compared to north of the equator, particularly at 10°W. Associated heat flux into the mixed layer could be as high as 138 W/m**2, but this depends strongly on the chosen depths where the upwelled water comes from. By combining upwelling velocities with sea surface temperature and productivity distributions, a mean monthly equatorial upwelling rate of 19 Sv was estimated for June 2006 and a biweekly mean of 24 Sv was estimated for September 2005.

Determination of hydrocarbon gases in mud volcanoes in the Sorokin Trough

Hydrocarbon gases were determined in sediments from three mud volcanoes in the Sorokin Trough. In comparison to a reference station outside the mud volcano area, the deposits are characterized by an enrichment of high-molecular hydrocarbons (C2-C4), an absence of unsaturated homologues, a predominance of iso-butane in comparison with n-butane, and the presence of gas hydrate. The molecular composition of the hydrocarbon gases suggests their deep sources and thermogenic origin. In the pelagic sediments at the reference station, the methane concentration is relatively low (up to 49 ml/l); maximum concentrations are reached in deposits of the Dvurechenskii mud volcano (up to 400 ml/l). It was the first time that gas hydrate was sampled at the Dvurechenskii mud volcano. The gas extracted by dissociation of hydrate samples was dominated by methane (99.5%) with low amounts of ethane and propane (less than 0.5%). The isotopic composition of the methane varies between -62 and -66 per mill PDB in d13C, and between -185 and -209 per mill SMOW in dD, indicating a mainly biogenic origin with an admixture of thermogenic gas.

Molecular and isotopic properties of gases from ODP Holes of ODP Leg 204

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C2+ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO2 and H2S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.

Noble gases in submarine pillow volcanic glasses

Fifteen submarine glasses from the East Pacific Rise (CYAMEX), the Kyushu-Palau Ridge (DSDP Leg 59) and the Nauru Basin (DSDP Leg 61) were analysed for noble gas contents and isotopic ratios. Both the East Pacific Rise and Kyushu-Palau Ridge samples showed Ne excess relative to Ar and a monotonic decrease from Xe to Ar when compared with air noble gas abundance. This characteristic noble gas abundance pattern (type 2, classified by Ozima and Alexander) is interpreted to be due to a two-stage degassing from a noble gas reservoir with originally atmospheric abundance. In the Kyushu-Palau Ridge sample, noble gases are nearly ten times more abundant than in the East Pacific Rise samples. This may be attributed to an oceanic crust contamination in the former mantle source. There is no correlation between the He content and that of the other noble gas in the CYAMEX samples. This suggests that He was derived from a larger region, independent from the other noble gases. Except where radiogenic isotopes are involved, all other noble gas isotopic ratios were indistinguishable from air noble gas isotopic ratios. The 3He/4He in the East Pacific Rise shows a remarkably uniform ratio of (1.21 +/- 0.07)*10**-5, while the40Ar/36Ar ranges from 700 to 5600.

Distribution of organic matter and gases in sediments at DSP Leg 63 Holes

As part of our continuing organic geochemical studies of sediments recovered by the Deep Sea Drilling Project, we have analyzed the types, amounts, and thermal alteration indices of organic matter in samples collected from the California continental margin on Leg 63. Some of the samples were frozen core; others were canned on site. Canned samples were analyzed for gas content using methods described by Mclver (1972). Our main objective was to see if the changes in surface circulation that had occurred through time off the California coast were reflected in changes in the type and amount of organic matter accumulating on the sea floor.