南海北部莺歌海岭头岬近岸烃类渗漏喷口分布及气体地球化学

Natural hydrocarbon seeps in a marine environment are one of the important contributors to greenhouse gases in the atmosphere,including methane,which is significant to the global carbon cycling and climate change.Four hydrocarbon seep areas,the Lingtou Promontory,the Yinggehai Rivulet mouth,the Yazhou Bay and the Nanshan Promontory,occurring in the Yinggehai Basin delineate a near-shore gas bubble zone.The gas composition and geochemistry of venting bubbles and the spatial distribution of hydrocarbon seeps are surveyed on the near-shore Lingtou Promontory.The gas composition of the venting bubbles is mainly composed of CO_2,CH_4,N_2 and O_2,with minor amounts of non-methane hydrocarbons.The difference in the bubbles' composition is a possible consequence of gas exchange during bubble ascent.The seepage gases from the seafloor are characterized by a high CO_2 content(67.35%) and relatively positive δ~(13)C_(V_PDB) values(-0.49×10~(-3)-0.86×10~(-3)),indicating that the CO_2 is of inorganic origin.The relatively low CH_4 content(23%) and their negative δ~(13)C_(V-PDB) values(-34.43×10~(-3)--37.53×10~(-3)) and high ratios of C_1 content to C_(1-5) one(0.98-0.99)as well point to thermogenic gases.The hydrocarbon seeps on the 3.5 Hz sub-bottom profile display a linear arrangement and are sub-parallel to the No.1 fault,suggesting that the hydrocarbon seeps may be associated with fracture activity or weak zones and that the seepage gases migrate laterally from the central depression of the Yinggehai Basin.     

Variability of gas composition and flux intensity in natural marine hydrocarbon seeps

The relationship between surface bubble composition and gas flux to the atmosphere was examined at five large seeps from the Coal Oil Point seep field (Santa Barbara Channel, CA, USA). The field research was conducted using a flux buoy designed to simultaneously measure the surface bubbling gas flux and the buoy’s position with differential GPS, and to collect gas samples. Results show that the flux from the five seeps surveyed a total of 11 times ranged from 800–5,500 m³ day^?1. The spatial distribution of flux from the five seeps was well described by two lognormal distributions fitted to two flux ranges. The seafloor and sea surface composition of bubbles differed, with the seafloor bubbles containing significantly more CO₂ (3–25%) and less air (N₂ and O₂). At the sea surface, the mole fraction of N₂ correlated directly with O₂ (R ² = 0.95) and inversely with CH₄ (R ² = 0.97); the CO₂ content was reduced to the detection limit (<0.1%). These data demonstrate that the bubble composition is modified by gas exchange during ascent: dissolved air enters, and CO₂ and hydrocarbon gases leave the bubbles. The mean surface composition at the five seeps varied with water depth and gas flux, with more CH₄ and higher CH₄/N₂ ratios found in shallower seeps with higher flux. It is suggested that the CH₄/N₂ ratio is a good proxy for total or integrated gas loss from the rising bubbles, although additional study is needed before this ratio can be used quantitatively.     

Gas flux and carbonate occurrence at a shallow seep of thermogenic natural gas

The Coal Oil Point seep field located offshore Santa Barbara, CA, consists of dozens of named seeps, including a peripheral ～200 m² area known as Brian Seep, located in 10 m water depth. A single comprehensive survey of gas flux at Brian Seep yielded a methane release rate of ～450 moles of CH₄ per day, originating from 68 persistent gas vents and 23 intermittent vents, with gas flux among persistent vents displaying a log normal frequency distribution. A subsequent series of 33 repeat surveys conducted over a period of 6 months tracked eight persistent vents, and revealed substantial temporal variability in gas venting, with flux from each individual vent varying by more than a factor of 4. During wintertime surveys sediment was largely absent from the site, and carbonate concretions were exposed at the seafloor. The presence of the carbonates was unexpected, as the thermogenic seep gas contains 6.7% CO₂, which should act to dissolve carbonates. The average δ¹³C of the carbonates was ?29.2?±?2.8‰ VPDB, compared to a range of ?1.0 to +7.8‰ for CO₂ in the seep gas, indicating that CO₂ from the seep gas is quantitatively not as important as ¹³C-depleted bicarbonate derived from methane oxidation. Methane, with a δ¹³C of approximately ?43‰, is oxidized and the resulting inorganic carbon precipitates as high-magnesium calcite and other carbonate minerals. This finding is supported by ¹³C-depleted biomarkers typically associated with anaerobic methanotrophic archaea and their bacterial syntrophic partners in the carbonates (lipid biomarker δ¹³C ranged from ?84 to ?25‰). The inconsistency in δ¹³C between the carbonates and the seeping CO₂ was resolved by discovering pockets of gas trapped near the base of the sediment column with δ¹³C-CO₂ values ranging from ?26.9 to ?11.6‰. A mechanism of carbonate formation is proposed in which carbonates form near the sediment–bedrock interface during times of sufficient sediment coverage, in which anaerobic oxidation of methane is favored. Precipitation occurs at a sufficient distance from active venting for the molecular and isotopic composition of seep gas to be masked by the generation of carbonate alkalinity from anaerobic methane oxidation.

Authigenic carbonates related to active seepage of methane-rich hot brines at the Cheops mud volcano,Menes caldera (Nile deep-sea fan,eastern Mediterranean Sea)

On the passive margin of the Nile deep-sea fan, the active Cheops mud volcano (MV; ca. 1,500 m diameter, ~20–30 m above seafloor, 3,010–3,020 m water depth) comprises a crater lake with hot (up to ca. 42 °C) methane-rich muddy brines in places overflowing down the MV flanks. During the Medeco2 cruise in fall 2007, ROV dives enabled detailed sampling of the brine fluid, bottom lake sediments at ca. 450 m lake depth, sub-surface sediments from the MV flanks, and carbonate crusts at the MV foot. Based on mineralogical, elemental and stable isotope analyses, this study aims at exploring the origin of the brine fluid and the key biogeochemical processes controlling the formation of these deep-sea authigenic carbonates. In addition to their patchy occurrence in crusts outcropping at the seafloor, authigenic carbonates occur as small concretions disseminated within sub-seafloor sediments, as well as in the bottom sediments and muddy brine of the crater lake. Aragonite and Mg-calcite dominate in the carbonate crusts and in sub-seafloor concretions at the MV foot, whereas Mg-calcite, dolomite and ankerite dominate in the muddy brine lake and in sub-seafloor concretions near the crater rim. The carbonate crusts and sub-seafloor concretions at the MV foot precipitated in isotopic equilibrium with bottom seawater temperature; their low δ¹³C values (–42.6 to –24.5‰) indicate that anaerobic oxidation of methane was the main driver of carbonate precipitation. By contrast, carbonates from the muddy lake brine, bottom lake concretions and crater rim concretions display much higher δ¹³C (up to –5.2‰) and low δ¹⁸O values (down to –2.8‰); this is consistent with their formation in warm fluids of deep origin characterized by ¹³C-rich CO₂ and, as confirmed by independent evidence, slightly higher heavy rare earth element signatures, the main driver of carbonate precipitation being methanogenesis. Moreover, the benthic activity within the seafloor sediment enhances aerobic oxidation of methane and of sulphide that promotes carbonate dissolution and gypsum precipitation. These findings imply that the coupling of carbon and sulphur microbial reactions represents the major link for the transfer of elements and for carbon isotope fractionation between fluids and authigenic minerals. A new challenge awaiting future studies in cold seep environments is to expand this work to oxidized and reduced sulphur authigenic minerals.     

Origin of the hydrocarbon gases carbon dioxide and hydrogen sulfide in Dodan Field (SE-Turkey)

Gas occurrences consisting of carbon dioxide (CO₂), hydrogen sulfide (H₂S), and hydrocarbon (HC) gases and oil within the Dodan Field in southeastern Turkey are located in Cretaceous carbonate reservoir rocks in the Garzan and Mardin Formations. The aim of this study was to determine gas composition and to define the origin of gases in Dodan Field. For this purpose, gas samples were analyzed for their molecular and isotopic composition. The isotopic composition of CO₂, with values of −1.5‰ and −2.8‰, suggested abiogenic origin from limestone. δ³⁴S values of H₂S ranged from +11.9 to +13.4‰. H₂S is most likely formed from thermochemical sulfate reduction (TSR) and bacterial sulfate reduction (BSR) within the Bakuk Formation. The Bakuk Formation is composed of a dolomite dominated carbonate succession also containing anhydrite. TSR may occur within an evaporitic environment at temperatures of approximately 120–145 °C. Basin modeling revealed that these temperatures were reached within the Bakuk Formation at 10 Ma. Furthermore, sulfate reducing bacteria were found in oil–water phase samples from Dodan Field. As a result, the H₂S in Dodan Field can be considered to have formed by BSR and TSR.As indicated by their isotopic composition, HC gases are of thermogenic origin and were generated within the Upper Permian Kas and Gomaniibrik Formations. As indicated by the heavier isotopic composition of methane and ethane, HC gases were later altered by TSR. Based on our results, the Dodan gas field may have formed as a result of the interaction of the following processes during the last 7–8 Ma: 1) thermogenic gas generation in Permian source rocks, 2) the formation of thrust faults, 3) the lateral-up dip migration of HC-gases due to thrust faults from the Kas Formation into the Bakuk Formation, 4) the formation of H₂S and CO₂ by TSR within the Bakuk Formation, 5) the vertical migration of gases into reservoirs through the thrust fault, and 6) lateral-up dip migration within reservoir rocks toward the Dodan structure.     

Isotopic composition of gas hydrates in subsurface sediments from offshore Sakhalin Island, Sea of Okhotsk

Hydrate-bearing sediment cores were retrieved from recently discovered seepage sites located offshore Sakhalin Island in the Sea of Okhotsk. We obtained samples of natural gas hydrates and dissolved gas in pore water using a headspace gas method for determining their molecular and isotopic compositions. Molecular composition ratios C₁/_C2+ from all the seepage sites were in the range of 1,500–50,000, while δ¹³C and δD values of methane ranged from ?66.0 to ?63.2‰ VPDB and ?204.6 to ?196.7‰ VSMOW, respectively. These results indicate that the methane was produced by microbial reduction of CO₂. δ¹³C values of ethane and propane (i.e., ?40.8 to ?27.4‰ VPDB and ?41.3 to ?30.6‰ VPDB, respectively) showed that small amounts of thermogenic gas were mixed with microbial methane. We also analyzed the isotopic difference between hydrate-bound and dissolved gases, and discovered that the magnitude by which the δD hydrate gas was smaller than that of dissolved gas was in the range 4.3–16.6‰, while there were no differences in δ¹³C values. Based on isotopic fractionation of guest gas during the formation of gas hydrate, we conclude that the current gas in the pore water is the source of the gas hydrate at the VNIIOkeangeologia and Giselle Flare sites, but not the source of the gas hydrate at the Hieroglyph and KOPRI sites.     

Methane flux dynamics in relation to methanogenic and methanotrophic populations in the soil of Indian Sundarban mangroves

The dynamics of methane (CH₄) flux in relation to populations of methanogenic and methanotrophic bacteria was studied under the different biophysical conditions of the Indian Sundarban mangrove ecosystem. Soil depth profile analysis (up to 60 cm) in the lower littoral zone (LLZ) revealed that a methanogenic population of 6.45 ± 0.19 × 10⁴ cells/g dry weight (dry wt) of soil accounted for a CH₄ production rate of 6.23 ± 3.53 × 10³ µmol m^?2 day^?1, whereas in the surface soil, a methanogenic population of 3.34 ± 0.37 × 10⁴ cells/g dry wt of soil accounted for a CH₄ production rate of 31.6 ± 0.57 µmol m^?2 day^?1. The CH₄ oxidation rate at 60 cm depth in the LLZ was 24.42 ± 1.28 µmol m^?2 day^?1, with an average methanotrophic population of 1.33 ± 0.43 × 10⁴ cells/g dry wt of soil, whereas in the surface soil, the oxidation rate and average population were 3.38 ± 1.43 × 10³ µmol m^?2 day^?1 and 12.80 ± 2.54 × 10⁴ cells/g dry wt of soil, respectively. A similar soil profile in terms of CH₄ dynamics and the populations of methanogenic and methanotrophic bacteria was found in the mid‐littoral and upper littoral zones of the studied area. The results demonstrate that most of the produced CH₄ (approximately 60%) was oxidized by methanotrophic bacteria present in the soil, thus revealing their principal role in regulating the CH₄ flux from this unique ecosystem.     

Evidence of subsurface anaerobic biodegradation of hydrocarbons and potential secondary methanogenesis in terrestrial mud volcanoes

The assessment of gas origin in mud volcanoes and related petroleum systems must consider post-genetic processes which may alter the original molecular and isotopic composition of reservoir gas. Beyond eventual molecular and isotopic fractionation due to gas migration and microbial oxidation, investigated in previous studies, we now demonstrate that mud volcanoes can show signals of anaerobic biodegradation of natural gas and oil in the subsurface. A large set of gas geochemical data from more than 150 terrestrial mud volcanoes worldwide has been examined. Due to the very low amount of C₂₊ in mud volcanoes, isotopic ratios of ethane, propane and butane (generally the best tracers of anaerobic biodegradation) are only available in a few cases. However, it is observed that ¹³C-enriched propane is always associated with positive δ¹³C_CO2 values, which are known indicators of secondary methanogenesis following anaerobic biodegradation of petroleum. Data from carbon isotopic ratio of CO₂ are available for 134 onshore mud volcanoes from 9 countries (Azerbaijan, Georgia, Ukraine, Russia, Turkmenistan, Trinidad, Italy, Japan and Taiwan). Exactly 50% of mud volcanoes, all releasing thermogenic or mixed methane, show at least one sample with δ¹³C_CO2 > +5‰ (PDB). Thermogenic CH₄ associated with positive carbon isotopic ratio of CO₂ generally maintains its δ¹³C-enriched signature, which is therefore not perturbed by the lighter secondary microbial gas. There is, however, high variability in the δ¹³C_CO2 values within the same mud volcanoes, so that positive δ¹³C_CO2 values can be found in some vents and not in others, or not continuously in the same vent. This can be due to high sensitivity of δ¹³C_CO2 to gas–water–rock interactions or to the presence of differently biodegraded seepage systems in the same mud volcano. However, finding a positive δ¹³C_CO2 value should be considered highly indicative of anaerobic biodegradation and further analyses should be made, especially if mud volcanoes are to be used as pathfinders of the conditions indicative of subsurface hydrocarbon accumulations in unexplored areas.     

冲绳海槽浮岩中碳、氢同位素组成特征

利用分阶段热解释放气体质谱分析法研究了冲绳海槽浮岩热解释放气中CO₂和H₂O的碳、氢同位素组成,结果显示:浮岩中原生CO₂和H₂O主要释放于400～1 000℃,CO₂的碳同位素组成介于-6.7×10-3～-22.7×10-3,H₂O的氢同位素组成从-45×10-3变到-71×10-3,均落入幔源火山岩的变化范围,而且浮岩的氢同位素组成与海槽区玄武岩的氢同位素组成非常接近,这表明冲绳海槽浮岩与玄武岩之间具有密切的成因联系,浮岩岩浆和玄武岩岩浆是同源岩浆不同程度结晶分异的产物.另外,这些浮岩较洋中脊玄武岩要贫13C,并富集D,同时具有从洋中脊玄武岩向岛弧玄武岩变化的趋势,这表明浮岩岩浆在形成或上升过程中可能受到俯冲板块释放流体的影响.     

Methane in the Sevastopol coastal area, Black Sea

Concentrations of dissolved methane in seawater and bottom sediments, as well as of methane emanating from gas seeps were measured at 18 stations including several small bays in the Sevastopol coastal area (Black Sea) during 2007–2008. Methane concentrations in surface waters ranged from 10 to 2,970 nmol l^?1, and correlated well with values recorded for sediments. Methane concentrations in the water column were influenced by water depth, as well as by air and water temperatures. In the spring and summer of 2008, in situ CH₄ saturation relative to air was in the range of 970–71,900%. Maximum saturation was in summer. CH₄ fluxes to the atmosphere from the Sevastopol coastal area were estimated to vary from 190 to 1,550 μmol m^?2 day^?1. Gas bubbles escaping from the seepages contained about 57 vol% methane. Radiocarbon dating of the methane revealed an age not exceeding 150 years, implying a biogenic origin.     

Isotopic composition of dissolved inorganic carbon in subsurface sediments of gas hydrate-bearing mud volcanoes, Lake Baikal: implications for methane and carbonate origin

We report on the isotopic composition of dissolved inorganic carbon (DIC) in pore-water samples recovered by gravity coring from near-bottom sediments at gas hydrate-bearing mud volcanoes/gas flares (Malenky, Peschanka, Peschanka 2, Goloustnoe, and Irkutsk) in the Southern Basin of Lake Baikal. The δ¹³C values of DIC become heavier with increasing subbottom depth, and vary between ?9.5 and +21.4‰ PDB. Enrichment of DIC in ¹³C indicates active methane generation in anaerobic environments near the lake bottom. These data confirm our previous assumption that crystallization of carbonates (siderites) in subsurface sediments is a result of methane generation. Types of methanogenesis (microbial methyl-type fermentation versus CO₂-reduction) were revealed by determining the offset of δ¹³C between dissolved CH₄ and CO₂, and also by using δ¹³C and δD values of dissolved methane present in the pore waters. Results show that both mechanisms are most likely responsible for methane generation at the investigated locations.     

The structural features and petroleum resource potential of basins in the western and northwestern Australian margins

The oil and gas basins of Australia are confined to its western and northwestern margins. They are typical pericontinental depressions in the continent-ocean transition zone with a passive tectonic regime. The following oil and gas basins are definable from the south to northward: the Perth, Carnarvon, Canning, Browse, and Bonaparte. All these basins are well studied. Among them, the Carnarvon basin is the most productive. Despite the discovery of approximately a hundred oil and gas fields in this basin, its continental slopes are still insufficiently known. In this connection, the morphostructural features of the productive areas were analyzed using a specialized GIS technique. The performed analysis of the Carnarvon hydrocarbon-bearing basin demonstrated the efficiency of this technique and allowed several promising zones located west, north, and south of the discovered oil and gas fields and forming a single trend with them to be outlined. The total reserves of the country are as high as 2.1 × 10⁹ t of oil and 840 × 10⁹ m³ of gas. The annual oil production in Australia by January 1, 2008 was 22.25 × 10⁶ t of oil and 14 × 10⁹ m³ of gas. Approximately 95% of the oil and 80% of the gas produced in Australia by the beginning of 2008 were obtained from offshore parts of its basins.     

Ongoing methane discharge at well site 22/4b (North Sea) and discovery of a spiral vortex bubble plume motion

First direct evidence for ongoing gas seepage activity on the abandoned well site 22/4b (Northern North Sea, 57°55′ N, 01°38′ E) and discovery of neighboring seepage activity is provided from observations since 2005. A manned submersible dive in 2006 discovered several extraordinary intense seepage sites within a 60 m wide and 20 m deep crater cut into the flat 96 m deep seafloor. Capture and (isotope) chemical analyses of the gas bubbles near the seafloor revealed in situ concentrations of methane between 88 and 90%Vol. with δ¹³C–CH₄ values around −74‰ VPDB, indicating a biogenic origin. Bulk methane concentrations throughout the water column were assessed by 120 Niskin water samples showing up to 400.000 nM CH₄ in the crater at depth. In contrast, concentrations above the thermocline were orders of magnitude lower, with a median value of 20 nM. A dye tracer injection into the gas seeps revealed upwelling bubble and water motion with gas plume rise velocities up to ∼1 ms⁻¹ (determined near the seabed). However, the dissolved dye did not pass the thermocline, but returned down to the seabed. Measurements of direct bubble-mediated atmospheric flux revealed low values of 0.7 ± 0.3 kty⁻¹, much less than current state-of-the-art bubble dissolution models would predict for such a strong and upwelling in situ gas bubble flux at shallow water depths (i.e. ∼100 m).Acoustic multibeam water column imaging data indicate a pronounced 200 m lateral intrusion at the thermocline together with high methane concentration at this layer. A partly downward-orientated bubble plume motion is also visible in the acoustic data with potential short-circuiting in accordance to the dye experiment. This observation could partly explain the observed trapping of most of the released gas below the well-established thermocline in the North Sea. Moreover, 3D analyses of the multibeam water column data reveal that the upwelling plume transforms into a spiral expanding vortex while rising through the water column. Such a spiral vortex motion has never been reported before for marine gas seepage and might represent an important process with strong implication on plume dynamics, dissolution behavior, gas escape to the atmosphere, and is considered very important for respective modeling approaches.     

Molecular signals for anaerobic methane oxidation in Black Sea seep carbonates and a microbial mat

Linked to gas seeps on the Ukrainian shelf (northwestern Black Sea), massive authigenic carbonates form as a result of anaerobic methane oxidation. Lipid distributions in these ‘cold seep’ carbonates and an associated microbial mat were investigated for process markers reflecting the presence and metabolic activity of distinctive methane-related biota. The samples contain free, irregular isoprenoid hydrocarbons, namely the tail-to-tail linked acyclic C₂₀-isoprenoid 2,6,11,15-tetramethylhexadecane (crocetane), its C₂₅-homologue 2,6,10,15,19-pentamethylicosane (PMI), and several unsaturated derivatives thereof. Furthermore, specific acyclic and cyclic C₄₀-isoprenoids were released upon ether cleavage of the polar fraction from the carbonate. The abundance of these compounds indicates a pronounced role of particular Archaea in the biogeochemical cycling of carbon at methane seeps. Stable carbon isotopic analyses of these lipids reveal extraordinary depletions in ¹³C corresponding to δ-values in the range of −100±30‰ PDB, whereas other compounds show isotopic compositions normally observed for marine lipids (around −30‰ PDB). The isotope data imply that the biosynthesis of the archaeal isoprenoids occurred in situ and involved the utilization of isotopically depleted, i.e. methane-derived, carbon. Apart from archaeal markers, the carbonate and the mat contain authigenic, framboidal pyrite and isotopically depleted fatty acids, namely iso-, and anteiso-branched compounds most likely derived from sulphate-reducing bacteria (SRB). The indications for a tight association of these normally competitive organisms support a model invoking a syntrophic relationship of SRB with Archaea responsible for the anaerobic oxidation of methane. The biomarker patterns obtained from the Black Sea samples were further compared to those from a Oligocene seep carbonate (Lincoln Creek Formation, WA, USA) in order to evaluate their biomarker potential for ancient settings. The prominent occurrence of isotopically light crocetane (−112‰) and PMI (−120‰) meets the findings for the contemporary materials. Thus, isotopically depleted isoprenoids provide diagenetically stable fingerprints for the reconstruction of carbon cycling in both, modern and ancient methane seep systems.     

Stable carbon isotopic ratios of CH4-CO2-bearing fluid inclusions in fracture-fill mineralization from the Lower Saxony Basin (Germany) - A tool for tracing gas sources and maturity

The stable carbon isotopic ratios (δ¹³C) of methane (CH₄) and carbon dioxide (CO₂) of gas-rich fluid inclusions hosted in fracture-fill mineralization from the southern part of the Lower Saxony Basin, Germany have been measured online using a crushing device interfaced to an isotopic ratio mass spectrometer (IRMS). The data reveal that CH₄ trapped in inclusions seems to be derived from different source rocks with different organic matter types. The δ¹³C values of CH₄ in inclusions in quartz hosted by Carboniferous rocks range between −25 and −19‰, suggesting high-maturity coals as the source of methane. Methane in fluid inclusions in minerals hosted by Mesozoic strata has more negative carbon isotope ratios (−45 to −31‰) and appears to represent primary cracking products from type II kerogens, i.e., marine shales. There is a positive correlation between increasing homogenization temperatures of aqueous fluid inclusions and less negative δ¹³C(CH₄) values of in co-genetic gas inclusions probably indicating different mtaturity of the potential source rocks at the time the fluids were released. The CO₂ isotopic composition of CH₄-CO₂-bearing inclusions shows slight negative or even positive δ¹³C values indicating an inorganic source (e.g., water-rock interaction and dissolution of detrital, marine calcite) for CO₂ in inclusions. We conclude that the δ¹³C isotopic ratios of CH₄-CO₂-bearing fluid inclusions can be used to trace migration pathways, sources of gases, and alteration processes. Furthermore, the δ¹³C values of methane can be used to estimate the maturity of the rocks from which it was sourced. Results presented here are further supported by organic geochemical analysis of surface bitumens which coexist with the gas inclusion-rich fracture-fill mineralization and confirm the isotopic interpretations with respect to fluid source, type and maturity.     

Plankton carbon metabolism and air–water CO2 fluxes at a hypereutrophic tropical estuary

Multiple biotic and abiotic drivers regulate the balance between CO₂ assimilation and release in surface waters. In the present study, we compared in situ measurements of plankton carbon metabolism (primary production and respiration) to calculated air–water CO₂ fluxes (based on abiotic parameters) during 1 year (2008) in a hypereutrophic tropical estuary (Recife Harbor, NE Brazil – 08°03′S, 34°52′W) to test the hypothesis that high productivity leads to a net CO₂ flux from the atmosphere. The calculated CO₂ fluxes through the air–water interface (FCO₂) were negative throughout the year (FCO₂: –2 to –9 mmol C·m^?2·day^?1), indicating that Recife Harbor is an atmospheric CO₂ sink. Respiration rates of the plankton community ranged from 2 to 45 mmol C·m^?2·hr^?1. Gross primary production ranged from 0.2 to 281 mmol C·m^?2·hr^?1, exceeding respiration during most of the year (net autotrophy), except for the end of the wet season, when the water column was net heterotrophic. The present results highlight the importance of including eutrophic tropical shallow estuaries in global air–water CO₂ flux studies, in order to better understand their role as a sink of atmospheric CO₂.     

东海中北部海域秋季表层海水中无机碳与海气界面碳的迁移

基于2010 年11 月对长江口外东海中北部海域的综合调查, 系统研究了该海域的无机碳体系参数的分布特征、海?气界面二氧化碳通量及其影响因素。研究结果表明, 该海域秋季溶解无机碳(DIC)高值区主要出现在调查海域东北部及长江口附近海域, 而调查海域南部DIC 含量较少且变化平缓, 其主要是受台湾东部流向东北方向的黑潮支流及长江冲淡水的影响; 表层海水CO₂分压(pCO₂)值变化范围为40.8～63.5 Pa, 呈现沿黑潮支流流入方向由东南向西北逐渐增高的趋势。秋季表层海水pCO₂与温度(T)、盐度(S)有较好的负相关性, 说明海水温度升高和盐度增加, pCO₂降低, 反之亦然。另外, 通过估算得出, 秋季CO₂海-气交换通量为2.69～33.66 mmol/(m²·d), 平均值为(14.35 ± 7.06 )mmol/(m²·d),其在长江口邻近海域相对较大, 而在调查海域南部相对较小; 2010 年秋季水体向大气释放CO₂的量(以碳计)为(2.35 ± 1.16)×104 t/d, 是大气CO₂较强的源, 说明东海中北部海域秋季总体上是CO₂的源。     

Methane and methane carbon isotope ratios in the Northeast Atlantic including the Mid-Atlantic Ridge (50°N)

Previous work has shown that methane anomalies frequently occur within the rift valley of the Mid-Atlantic Ridge (MAR). The plumes appear confined within the high, steep walls of the valley, and it is not known whether methane may escape to the open ocean outside. In order to investigate this question, the concentration and ¹³C/¹²C ratio of methane together with CCl₃F concentration were measured in the northeastern Atlantic including the rift valley near 50°N. This segment contained methane plumes centered several 100 m above the valley floor with δ¹³C values mostly between –15‰ and –10‰. A limited number of helium isotope measurements showed that δ³He increased to 17% at the bottom of the valley, which suggests the helium and methane sources may be spatially separated. In the eastern Atlantic away from the ridge (48°N, 20°W), the methane concentration decreased monotonically from the surface to the bottom, but the methane δ¹³C exhibited a mid-water maximum of about –25‰. The bottom water methane contained a significantly lower δ¹³C of about –36‰. Thus, it appears that isotopically heavy methane escapes from the MAR into North Atlantic Deep Water (NADW) that contacts the ridge crest while circulating to the east. The formation of NADW supplies isotopically light methane that dilutes the input of heavy carbon from the ridge. We employed a time-dependent box model to calculate the extent of isotope dilution and thereby the flux of MAR methane into the NADW circulation. The degree of methane oxidation, which affects the ¹³C/¹²C of methane through kinetic isotope fractionation, was estimated by comparing methane and CFC-11 model results with observations. The model calculations indicate a MAR methane source of about 0.06×10⁻⁹ mol L⁻¹ yr⁻¹ to waters at the depth of the ridge crest. Assuming this extends to a 500 m thick layer over half of the entire Atlantic, the amount of methane escaping from the MAR to the open ocean is estimated to be about 1×10⁹ mol yr⁻¹. The total production of methane within the rift valley is likely much greater than the flux from the valley to the outside because of local oxidation. This implies that serpentinization of ultramafic rocks supports much of methane production in the rift valley because the amount expected from basalt degassing in association with mantle helium (<0.6×10⁹ mol CH₄ yr⁻¹) is less than even the net amount escaping from the valley. The model results also indicate the methane specific oxidation rate is about 0.05 yr⁻¹ in open waters of the northern Atlantic.     

Carbon cycling within the upper methanogenic zone of continental rise sediments; An example from the methane-rich sediments overlying the Blake Ridge gas hydrate deposits

Data from piston cores collected from Carolina Rise and Blake Ridge, and from many DSDP/ODP sites indicate that extreme ¹³C-depletion of methane and ΣCO₂ occurs within the uppermost methanogenic zone of continental rise sediments. We infer that ¹³C-depleted methane is generated near the top of the methanogenic zone when carbon of ¹³C-depleted ΣCO₂, produced by microbially-mediated anaerobic methane oxidation, is recycled back to methane through CO₂ reduction. Interstitial water and gas samples were collected in 27 piston cores, 16 of which penetrated through the sulfate reduction zone into methane-bearing sediments of the Carolina Rise and Blake Ridge. Isotopic measurements (δ¹³C_CH4, δ¹³C_CO2, δD_CH4, and δD_H2O) indicate that this methane is microbial in origin, produced by microbially-mediated CO₂ reduction. Methane samples form two distinct isotopic pools. (1) Methane from a seafloor seep site shows a mean δ¹³C_CH4 value of − 69 ± 2%., mirroring values found at ≥ 160 mbsf from a nearby DSDP site. (2) Twenty, areally-separated sites (sample depth, 10 to 25 mbsf) have δ¹³C_CH4 values ranging from −85 to −103%., and δ¹³C_CO2 as negative as −48%.. The very low δ¹³C values from the methane and CO₂ pools highlight the importance of carbon cycling within continental rise sediments at and near the sulfate-methane boundary.     

Carbon isotopes in mollusk shell carbonates

Mollusk shells contain many isotopic clues about calcification physiology and environmental conditions at the time of shell formation. In this review, we use both published and unpublished data to discuss carbon isotopes in both bivalve and gastropod shell carbonates. Land snails construct their shells mainly from respired CO₂, and shell δ¹³C reflects the local mix of C3 and C4 plants consumed. Shell δ¹³C is typically >10‰ heavier than diet, probably because respiratory gas exchange discards CO₂, and retains the isotopically heavier HCO₃ ^?. Respired CO₂ contributes less to the shells of aquatic mollusks, because CO₂/O₂ ratios are usually higher in water than in air, leading to more replacement of respired CO₂ by environmental CO₂. Fluid exchange with the environment also brings additional dissolved inorganic carbon (DIC) into the calcification site. Shell δ¹³C is typically a few ‰ lower than ambient DIC, and often decreases with age. Shell δ¹³C retains clues about processes such as ecosystem metabolism and estuarine mixing. Ca²⁺ ATPase-based models of calcification physiology developed for corals and algae likely apply to mollusks, too, but lower pH and carbonic anhydrase at the calcification site probably suppress kinetic isotope effects. Carbon isotopes in biogenic carbonates are clearly complex, but cautious interpretation can provide a wealth of information, especially after vital effects are better understood.