Changes in the storage and sink of carbon dioxide in subsurface atmospheres controlled by climate-driven processes: the case of the Ojo Guareña karst system

A comprehensive environmental monitoring program was conducted in the Ojo Guareña cave system (Spain), one of the longest cave systems in Europe, to assess the magnitude of the spatiotemporal changes in carbon dioxide gas (CO2) in the cave–soil–atmosphere profile. The key climate-driven processes involved in gas exchange, primarily gas diffusion and cave ventilation due to advective forces, were characterized. The spatial distributions of both processes were described through measurements of CO2 and its carbon isotopic signal (δ13C[CO2]) from exterior, soil and cave air samples analyzed by cavity ring-down spectroscopy (CRDS). The trigger mechanisms of air advection (temperature or air density differences or barometric imbalances) were controlled by continuous logging systems. Radon monitoring was also used to characterize the changing airflow that results in a predictable seasonal or daily pattern of CO2 concentrations and its carbon isotopic signal. Large daily oscillations of CO2 levels, ranging from 680 to 1900 ppm day−1 on average, were registered during the daily oscillations of the exterior air temperature around the cave air temperature. These daily variations in CO2 concentration were unobservable once the outside air temperature was continuously below the cave temperature and a prevailing advective-renewal of cave air was established, such that the daily-averaged concentrations of CO2 reached minimum values close to atmospheric background. The daily pulses of CO2 and other tracer gases such as radon (222Rn) were smoothed in the inner cave locations, where fluctuation of both gases was primarily correlated with medium-term changes in air pressure. A pooled analysis of these data provided evidence that atmospheric air that is inhaled into dynamically ventilated caves can then return to the lower troposphere as CO2-rich cave air.

Pore accessibility by methane and carbon dioxide in coal as determined by neutron scattering

Contrast-matching ultrasmall-angle neutron scattering (USANS) and small-angle neutron scattering (SANS) techniques were used for the first time to determine both the total pore volume and the fraction of the pore volume that is inaccessible to deuterated methane, CD4, in four bituminous coals in the range of pore sizes between ∼10 Å and ∼5 μm. Two samples originated from the Illinois Basin in the U.S.A., and the other two samples were commercial Australian bituminous coals from the Bowen Basin. The total and inaccessible porosity were determined in each coal using both Porod invariant and the polydisperse spherical particle (PDSP) model analysis of the scattering data acquired from coals both in vacuum and at the pressure of CD4, at which the scattering length density of the pore-saturating fluid is equal to that of the solid coal matrix (zero average contrast pressure). The total porosity of the coals studied ranged from 7 to 13%, and the volume of pores inaccessible to CD4 varied from ∼13 to ∼36% of the total pore volume. The volume fraction of inaccessible pores shows no correlation with the maceral composition; however, it increases with a decreasing total pore volume. In situ measurements of the structure of one coal saturated with CO2 and CD4 were conducted as a function of the pressure in the range of 1−400 bar. The neutron scattering intensity from small pores with radii less than 35 Å in this coal increased sharply immediately after the fluid injection for both gases, which demonstrates strong condensation and densification of the invading subcritical CO2 and supercritical methane in small pores.

Solubilities of palmitic and stearic fatty acids in supercritical carbon dioxide

The solubilities of two fatty acids, namely hexadecanoic acid (palmitic acid) and octadecanoic acid (stearic acid) in supercritical carbon dioxide (SCCO2), were determined at T = (328 and 338) K from 12.8 MPa to 22.6 MPa. Three models, namely a thermodynamic model based on the Peng-Robinson equation of state with Kwak and Mansoori mixing rules, a model based on dilute solution theory proposed by Mendez-Santiago and Teja and a new reformulated Chrastil equation model, were used to correlate the solubilities. In all the models, the correlation constants are temperature independent. All the models successfully correlated the experimental results for the solubilities of hexadecanoic acid within 3%.

Absolute Entropy and Energy of Carbon Dioxide Using the Two-Phase Thermodynamic Model

The two-phase thermodynamic (2PT) model is used to determine the absolute entropy and energy of carbon dioxide over a wide range of conditions from molecular dynamics trajectories. The 2PT method determines the thermodynamic properties by applying the proper statistical mechanical partition function to the normal modes of a fluid. The vibrational density of state (DoS), obtained from the Fourier transform of the velocity autocorrelation function, converges quickly, allowing the free energy, entropy, and other thermodynamic properties to be determined from short 20-ps MD trajectories. The anharmonic effects in the vibrations are accounted for by the broadening of the normal modes into bands from sampling the velocities over the trajectory. The low frequency diffusive modes, which lead to finite DoS at zero frequency, are accounted for by considering the DoS as a superposition of gas-phase and solid-phase components (two phases). The analytical decomposition of the DoS allows for an evaluation of properties contributed by different types of molecular motions. We show that this 2PT analysis leads to accurate predictions of entropy and energy of CO2 over a wide range of conditions (from the triple point to the critical point of both the vapor and the liquid phases along the saturation line). This allows the equation of state of CO2 to be determined, which is limited only by the accuracy of the force field. We also validated that the 2PT entropy agrees with that determined from thermodynamic integration, but 2PT requires only a fraction of the time. A complication for CO2 is that its equilibrium configuration is linear, which would have only two rotational modes, but during the dynamics it is never exactly linear, so that there is a third mode from rotational about the axis. In this work, we show how to treat such linear molecules in the 2PT framework.

Deepwater and Other Sharks of the U.S. Atlantic Ocean Exclusive Economic Zone

Fifty-one deepwater and other shark species of the U.S. Exclusive Economic Zone in the Atlantic Ocean and Gulf of Mexico, which currently are not included in any Federal fishery management plan, are described, with a focus on primary distribution. Many of these shark species are not well known, while others which are more common may be of particular interest. Owing to concerns regarding possible increases in fishing effort for some of these species, as well as possible increases in bycatch rates as other fisheries move farther offshore, it is important that these sharks be considered in marine ecosystem management efforts. This will necessitate a better understanding of their biology and distribution. Primary distribution maps are included, based on geographic information system (GIS) analyses of both published and unpublished data, and a review of the literature. The most recent systematic classification and nomenclature for these species is used.

Boat wakes and their influence on erosion in the Atlantic Intracoastal Waterway, North Carolina

Boat wakes in the Atlantic Intracoastal Waterway (AIWW) of North Carolina occur in environments not normally subjected to (wind) wave events, making sections of AIWW potentially vulnerable to extreme wave events generated by boat wakes. The Snow’s Cut area that links the Cape Fear River to the AIWW is an area identified by the Wilmington District of the U.S. Army Corps of Engineers as having significant erosion issues; it was hypothesized that this erosion could be being exacerbated by boat wakes. We compared the boat wakes for six combinations of boat length and speed with the top 5% wind events. We also computed the benthic shear stress associated with boat wakes and whether sediment would move (erode) under those conditions. Finally, we compared the transit time across Snow’s Cut for each speed. We focused on two size classes of V-hulled boats (7 and 16m) representative of AIWW traffic and on three boat speeds (3, 10 and 20 knots). We found that at 10 knots when the boat was plowing and not yet on plane, boat wake height and potential erosion was greatest. Wakes and forecast erosion were slightly mitigated at higher, planing speeds. Vessel speeds greater than 7 knots were forecast to generate wakes and sediment movement zones greatly exceeding that arising from natural wind events. We posit that vessels larger than 7m in length transiting Snow’s Cut (and likely many other fetch-restricted areas of the AIWW) frequently generate wakes of heights that result in sediment movement over large extents of the AIWW nearshore area, substantially in exceedance of natural wind wave events. If the speed, particularly of large V-hulled vessels (here represented by the 16m length class), were reduced to pre-plowing levels (~ 7 knots down from 20), transit times for Snow’s Cut would be increased approximately 10 minutes but based on our simulations would likely substantially reduce the creation of erosion-generating boat wakes. It is likely that boat wakes significantly exceed wind wave background for much of the AIWW and similar analyses may be useful in identifying management options.

Atmospheric carbon dioxide and the climatic record

This paper is an attempt to provide a summary review of conclusions from previous studies on this subject. They have been organized under the following subject headings: Conceptualization of the greenhouse effect; The climatic effect of doubled carbon dioxide; Interpretation of the climatic record; Diagnosis of apparent and possible model deficiencies; The paleoclimatic record.

Predation of tuna longline catches in the Indian Ocean, by killer-whales and sharks

Since the inception of the tuna long line fishery in the Indian Ocean in 1952, an annual average of 10% of the number of tunas and spear fishes caught continues to be damaged by sharks. In spite of the fact that this method of fishing for tunas is also resulting in the exploitation of a significant quantity of the tuna-preying sharks, the extent of the damage by these predators continues to be fairly constant. Quite often the damaged tunas are acceptable to the market, especially for canning. On the other hand report of damage caused by killer-whales, occasional at the beginning of the fishery in the Indian Ocean, has been increasing in frequency each year and since 1960 tuna fishermen have been desperately calling for ways and means of reducing the damage caused by these mammals. Unlike sharks killer-whales do not get hooked on the tuna long line; and tunas damaged by killer-whales are almost always unfit even for canning. The problem of predation by killer-whales exists not only in the whole of the Indian Ocean including the Timor and Banda Seas but also in the Atlantic and Pacific Oceans, especially in the seas around New Guinea, Samoa, Caroline and Marshal Islands. The seriousness of this problem of predation was highlighted at the annual tuna research conference held in Kochi, Japan, in February 1963, and steps were taken to devote considerable attention to this problem.

Replacement of methane from quartz sand-bearing hydrate with carbon dioxide-in-water emulsion

The replacement of CH4 from its hydrate in quartz sand with 90:10, 70:30, and 50:50 (W-CO2:W-H2O) carbon dioxide-in-water (C/W) emulsions and liquid CO2 has been performed in a cell with size of empty set 36 x 200 mm. The above emulsions were formed in a new emulsifier, in which the temperature and pressure were 285.2 K and 30 MPa, respectively, and the emulsions were stable for 7-12 h. The results of replacing showed that 13.1-27.1%, 14.1-25.5%, and 14.6-24.3% of CH4 had been displaced from its hydrate with the above emulsions after 24-96 It of replacement, corresponding to about 1.5 times the CH4 replaced with high-pressure liquid CO2. The results also showed that the replacement rate of CH4 with the above emulsions and liquid CO2 decreased from 0.543, 0.587, 0.608, and 0.348 1/h to 0.083, 0.077, 0.069, and 0.063 1/h with the replacement time increased from 24 to 96 h. It has been indicated by this study that the use of CO2 emulsions is advantageous compared to the use of liquid CO2 in replacing CH4 from its hydrate.

Main geochemical characteristics and key biogeochemical carbon processes in the East China Sea

Research related to carbon geochemistry and biogeochemistry in the East China Sea is reviewed in this paper. The East China Sea is an annual net sink for atmospheric CO, and a large net source of dissolved inorganic carbon to the ocean. The sea absorbs CO, from the atmosphere in spring and summer and releases it in autumn and winter. The East China Sea is a CO, sink in summer because Changjiang River freshwater flows into it. The net average sea-air interface carbon flux of the East China Sea is estimated to be about 4.3 X 10(6) t/y. Vertical carbon transport is mainly in the form of particulate organic carbon in spring; more than 98% of total carbon is transported in this form in surface water, and the number exceeds 68% in water near the bottom. In the southern East China Sea, the average particulate organic carbon inventory was about one-tenth that of the dissolved organic carbon. Research indicates that the southern Okinawa Trough is an important site for particulate organic carbon export from the shelf. The annual cross-shelf exports are estimated to be 414 and 106 Gmol/y for dissolved organic carbon and particulate organic carbon, respectively. Near-bottom transport could be the key process for shelf-to-deep sea export of biogenic and lithogenic particles.

Air–sea fluxes of oxygenated volatile organic compounds across the Atlantic Ocean

We present air-sea fluxes of oxygenated volatile organics compounds (OVOCs) quantified by eddy covariance (EC) during the Atlantic Meridional Transect cruise in 2012. Measurements of acetone, acetaldehyde, and methanol in air as well as in water were made in several different oceanic provinces and over a wide range of wind speeds (1-18 m s(-1)). The ocean appears to be a net sink for acetone in the higher latitudes of the North Atlantic but a source in the subtropics. In the South Atlantic, seawater acetone was near saturation relative to the atmosphere, resulting in essentially zero net flux. For acetaldehyde, the two-layer model predicts a small oceanic emission, which was not well resolved by the EC method. Chemical enhancement of air-sea acetaldehyde exchange due to aqueous hydration appears to be minor. The deposition velocity of methanol correlates linearly with the transfer velocity of sensible heat, confirming predominant airside control. We examine the relationships between the OVOC concentrations in air as well as in water, and quantify the gross emission and deposition fluxes of these gases.

Both respiration and photosynthesis determine the scaling of plankton metabolism in the oligotrophic ocean

Despite its importance to ocean–climate interactions, the metabolic state of the oligotrophic ocean has remained controversial for 415 years. Positions in the debate are that it is either hetero- or autotrophic, which suggests either substantial unaccounted for organic matter inputs, or that all available photosynthesis (P) estimations (including 14C) are biased. Here we show the existence of systematic differences in the metabolic state of the North (heterotrophic) and South (autotrophic) Atlantic oligotrophic gyres, resulting from differences in both P and respiration (R). The oligotrophic ocean is neither auto- nor heterotrophic, but functionally diverse. Our results show that the scaling of plankton metabolism by generalized P:R relationships that has sustained the debate is biased, and indicate that the variability of R, and not only of P, needs to be considered in regional estimations of the ocean’s metabolic state.

Depth-related gradients in community structure and relatedness of bivalves and isopods in the Southern Ocean.

Despite increased research over the last decade, diversity patterns in Antarctic deep-sea benthic taxa and their driving forces are only marginally known. Depth-related patterns of diversity and distribution of isopods and bivalves collected in the Atlantic sector of the Southern Ocean are analysed. The data, sampled by epibenthic sledge at 40 deep-sea stations from the upper continental slope to the hadal zone (774 – 6348 m) over a wide area of the Southern Ocean, comprises 619 species of isopods and 81 species of bivalves,. There were more species of isopods than bivalves in all samples, and species per station varied from 2 to 85 for isopods and from 0 to 18 for bivalves. Most species were rare, with 72% of isopod species restricted to one or two stations, and 45% of bivalves. Among less-rare species bivalves tended to have wider distributions than isopods. The species richness of isopods varied with depth, showing a weak unimodal curve with a peak at 2000 – 4000 m, while the richness of bivalves did not. Multivariate analyses indicate that there are two main assemblages in the Southern Ocean, one shallow and one deep. These overlap over a large depth-range (2000 – 4000 m). Comparing analyses based on the Sørensen resemblance measure (presence/absence) and Γ+ (presence/absence incorporating relatedness among species) indicates that rare species tend to have other closely related species within the same depth band. Analysis of relatedness among species indicates that the taxonomic variety of bivalves tends to decline at depth, whereas that of isopods is maintained. This, it is speculated, may indicate that the available energy at depth is insufficient to maintain a range of bivalve life-history strategies

Dynamics and mixing in the Upper Ocean Layer

S'estudia la resposta de la capa de barreja oceànica al forçament atmosfèric considerant dades obtingudes durant 12 dies d'abril del 2001 a 42 estacions a través de l'Atlàntic nord seguint aproximadament la latitud de 53ºN. Aquestes dades inclouen, a més de variables atmosfèriques, mesures de CTD, velocitats amb ADCP i dades de microestructura obtingudes amb un perfilador de caiguda lliure. En aquest últim cas, s'han desenvolupat tècniques de processament de les dades que també es presenten aquí. El transsecte estudiat segueix la posició climatològica del rotacional mitjà anual del vent igual a zero i travessa el corrent del Labrador i algunes branques i meandres del Corrent Atlàntic Nord. El forçament atmosfèric es va caracteritzar per vents intensos i fluxos superficials de calor negatius, tot i que, tal com es dedueix de la comparació del gruix de la capa de barreja amb la longitud de Monin-Obukov, la barreja induïda pel vent va dominar sobre la convectiva durant tot el transsecte.