Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.     

Marine hydrocarbon source rocks of the Upper Permian Longtan Formation and their contribution to gas accumulation in the northeastern Sichuan Basin,southwest China

Identification of the main hydrocarbon source rocks of the large Puguang gas field (northeastern Sichuan Basin, southwest China) has been the subject of much discussion in recent years. A key aspect has been the lack of a comprehensive understanding of the development of hydrocarbon source rocks of the Upper Permian Longtan Formation, which had been thought to contain mainly coal seams and thick carbonate layers. In this paper, based on geological data from more than ten wells and outcrops and their related mineralogy and geochemistry, we investigated the depositional environment and main factors controlling organic matter enrichment in the Longtan Formation. We propose a model which combines information on the geological environment and biological changes over time. In the model, organic matter from prolific phytoplankton blooms was deposited in quiescent platform interior sags with rising sea-levels. During the Longtan period, the area from Bazhong to Dazhou was a platform interior sag with relatively deep water and a closed environment, which was controlled by multiple factors including syngenetic fault settling, isolation of submarine uplifts and rising sea-levels leading to water column stratification. Although the bottom water was anoxic, the phytoplankton were able to bloom in the well-lit upper euphotic zone thus giving rise to a set of sapropelic black shales and marlstones containing mostly algal organic matter with minor terrestrial contributions. As a consequence, these rocks have a high hydrocarbon generation potentials and can be classified as high-quality source rocks. The area from Bazhong to Dazhou is a center of hydrocarbon generation, being the main source of reservoired paleo-oils and presently discovered as pyrobitumen in the Puguang gas field. The identification of these source rocks is very important to guide future petroleum exploration in the northeastern Sichuan Basin.     

Effects of CO2 on benthic biota: An in situ benthic chamber experiment in Storfjorden (Norway)

Carbon capture and storage (CCS) methods, either sub-seabed or in ocean depths, introduces risk of CO₂ leakage and subsequent interaction with the ecosystem. It is therefore important to obtain information on possible effects of CO₂. In situ CO₂ exposure experiments were carried out twice for 10 days during 2005 using a Benthic Chamber system at 400 m depth in Storfjorden, Norway. pCO₂ in the water above the sediment in the chambers was controlled at approximately 500, 5000 and 20,000 μatm, respectively. This article describes the experiment and the results from measured the biological responses within the chamber sediments. The results show effects of elevated CO₂ concentrations on biological processes such as increased nanobenthos density. Methane production and sulphate reduction was enhanced in the approximately 5000 μatm chamber.     

南海北部海底沉积物在温度变化下的三种声速类型

研究南海北部海底沉积物温度变化状态下声速性质,得出以下结论:(1) 南海北部海底沉积物具有声速温度正增长(STPIK)、声速温度负增长(STNIK)和声速温度波动(STWK)三种类型,后两种类型在世界其他范围内海域未见报道.(2) 声速温度正增长类型和声速温度负增长类型沉积物的温度变化对声速影响都具有十分显著的线性关系,但是原状样品由于组成不均匀性,增大了声速的非线性变化.(3)南海北部海底沉积物的孔隙度、密度等主要物理参数差异不明显,难以直接解释三类样品的温度-声速性质的不同.(4)对于STPIK类型沉积物,理论分析与实验结果的统一性,可以运用海底沉积物与海水声速比进行校正不同温度状态下的海底沉积物的声速.(5)对于STNIK和STWK类型沉积物,需要深入研究,从理论和实验角度揭开其机理和成因.海底沉积物声速-温度特性研究将为提高南海北部海域天然气水合物声学探测精度和准确度提供声速性质依据.     

Structural controls on the formation of BSR over a diapiric anticline from a dense MCS survey offshore southwestern Taiwan

A dense seismic reflection survey with up to 250-m line-spacing has been conducted in a 15 × 15 km wide area offshore southwestern Taiwan where Bottom Simulating Reflector is highly concentrated and geochemical signals for the presence of gas hydrate are strong. A complex interplay between north–south trending thrust faults and northwest–southeast oblique ramps exists in this region, leading to the formation of 3 plunging anticlines arranged in a relay pattern. Landward in the slope basin, a north–south trending diapiric fold, accompanied by bright reflections and numerous diffractions on the seismic profiles, extends across the entire survey area. This fold is bounded to the west by a minor east-verging back-thrust and assumes a symmetric shape, except at the northern and southern edges of this area, where it actively overrides the anticlines along a west-verging thrust, forming a duplex structure. A clear BSR is observed along 67% of the acquired profiles. The BSR is almost continuous in the slope basin but poorly imaged near the crest of the anticlines. Local geothermal gradient values estimated from BSR sub-bottom depths are low along the western limb and crest of the anticlines ranging from 40 to 50 °C/km, increase toward 50–60 °C/km in the slope basin and 55–65 °C/km along the diapiric fold, and reach maximum values of 70 °C/km at the southern tip of the Good Weather Ridge. Furthermore, the local dips of BSR and sedimentary strata that crosscut the BSR at intersections of any 2 seismic profiles have been computed. The stratigraphic dips indicated a dominant east–west shortening in the study area, but strata near the crest of the plunging anticlines generally strike to southwest almost perpendicular to the direction of plate convergence. The intensity of the estimated bedding-guided fluid and gas flux into the hydrate stability zone is weaker than 2 in the slope basin and the south-central half of the diapiric fold, increases to 7 in the northern half of the diapiric fold and plunging anticlines, and reaches a maximum of 16 at the western frontal thrust system. Rapid sedimentation, active tectonics and fluid migration paths with significant dissolved gas content impact on the mechanism for BSR formation and gas hydrate accumulation. As we begin to integrate the results from these studies, we are able to outline the regional variations, and discuss the importance of structural controls in the mechanisms leading to the gas hydrate emplacements.     

Authigenic carbonates from the eastern Black Sea as an archive for shallow gas hydrate dynamics – Results from the combination of CT imaging with mineralogical and stable isotope analyses

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area (“Batumi seep area”) located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups.     

Air-Sea Gas Transfer Velocity in Stormy Winter Estimated from Radon Deficiency

Thirteen vertical profiles of ²²⁶Ra and ²²²Rn in the near-surface water were obtained in the western North Pacific in winter, and the gas transfer velocities across the air-sea interface were estimated. The transfer velocities found by applying a steady state model varied widely from 2.1 to 30.2 m day⁻¹ with a mean of 9.4 m day⁻¹. The mean value is almost 5 times higher than that in summer in other oceans, and the maximum value is a record high for world oceans. This is partly due to the inadequacy of the steady state model, which overestimates when stronger winds blow in more recent days than the ²²²Rn half-life of about 4 days. In fact, a strong low pressure zone passed through the station about 2 days earlier, which was one of the low pressure zones that with a period of develop once a week or so in the northwestern North Pacific in winter. Instead of steady-state removal, if half of the radon removal occurred sporadically every 7 days, and the last removal took place two days before the observation, the transfer velocity would be 26 m day⁻¹. Our mean transfer velocity, which is less than 20% different from the steady state value including both overestimated and underestimated values, 9.4 ± 4.8 m day⁻¹, seems to represent the mean state of this region in winter. This suggests that the gas exchange fluxes under extremely rough conditions in the open ocean are larger than those estimated by using a transfer velocity equation with a linear or quadratic relationship with wind speed. This revised version was published online in July 2006 with corrections to the Cover Date.     

High-resolution shallow seismic identification of gas escape features in the sediments of Loch Tay, Scotland: tectonic and microbiological associations

High-resolution seismic reflection profiles (3·5 kHz) have revealed the presence of extensive interstitial gas accumulation within the sedimentary sequences of Loch Tay, Scotland, as identified by acoustic turbidity masking the seismic stratigraphy. Within the central section of the loch, in the deepest water area directly above the zone of the seismically active Loch Tay Fault, focused flows of gas through the sediment pile to the loch bed via chimneys and pockmarks, together with gas seeps within the water column, have been identified. Microbiological observations indicate that the gas is biogenic CH₄, produced by both chemoautotrophic (which use CO₂ as a source of carbon and H₂ as a source of energy) and aceticlastic species (which use acetate as a source of carbon and energy) of methanogens in the fine-grained, organic rich deposits that have been focused into the zone of accumulation in the deep central part of the loch. The spatial distribution of the gas escape features suggests that earthquake movements along the Loch Tay Fault are responsible for facilitating focused gas escape in this part of the loch, by the creation of new pathways and conduits through the sediment pile, along which gas can migrate upwards and exit into the water column. Relict pockmarks and associated chimneys identified in the seismic records indicate that gas escape has been taking place since Pleistocene times though the precise timings cannot be ascertained. This is the first time that such features have been reported from a lake in the UK.     

Paleo-oil reservoir pyrolysis and gas release in the Yangtze Block imply an alternative mechanism for the Late Permian Crisis

The causes of the global mass extinction that occurred around the Permian–Triassic boundary have been widely studied through the geological record and in various locations. The results show that volcanic activity was a key factor in initiating the crisis during the Late Permian. Compared to other thermal events triggered by volcanic activity, pyrolysis of petroleum in Pre-Permian reservoirs has rarely been suggested as a significant source of the greenhouse gases that caused the mass extinction. In this study, geochemical analysis is carried out of a huge paleo-oil reservoir in the Yangtze Block (YB), South China. The detection of mineral inclusions and pyrobitumens is evidence of rapid pyrolysis of accumulated oil in the Ediacaran reservoir. New evidence from hydrothermal minerals and the presence of domain mesophase in the pyrobitumen suggest that the pyrolysis process occurred abruptly and that greenhouse gases were rapidly released through venting pipes. The dating of such a complex geological event in this old and deeply buried reservoir is inevitably difficult and potentially unreliable. However, cross-validation of the multiple evidence sources, including hydrothermal minerals and domain mesophase, indicates that the rapid oil pyrolysis must have been driven by a major thermal event. Reconstruction of burial and thermal histories suggests that the thermal event was most likely to have been triggered by the Emeishan Large Igneous Province (ELIP), which was in a period of significant volcanic activity during the Late Permian. Massive volumes of gases, including methane, carbon dioxide, and possibly hydrogen sulfide, were released, causing a significant increase in greenhouse gases that may have contributed to global warming and the resulting mass extinction during the Late Permian Crisis (LPC).     

A numerical study on 2-D compressive wave propagation in rock masses with a set of joints along the radial direction normal to the joints

An explosion in a borehole or an accidental explosion in a tunnel will generate a two-dimensional (2-D) compressive wave that travels through the surrounding rock mass. For the problem of 2-D compressive wave propagation in a rock mass with parallel joints in the radial direction normal to the joints, parametric studies on the transmission ratio and the maximum rebound ratio are performed in universal distinct element code. The variation of the transmission ratio with the ratio of joint spacing to wavelength is generalized into a characteristic curve, which can be used as a prediction model for estimating the transmission ratio. The relationship between the maximum rebound ratio and the influence factors is obtained in charts. The charts can be used as a prediction model for estimating the maximum rebound ratio. The proposed prediction models for estimating the transmission ratio and the maximum rebound ratio are applied to a field explosion test, Mandai test in Singapore. The minimum possible values of peak particle velocity (PPV) at the monitoring points are estimated by using the proposed prediction model for estimating the transmission ratio along the radial direction normal to the joints. On the other hand, the maximum possible values of PPV are estimated by using the proposed prediction model for estimating the maximum rebound ratio along the same radial direction. The comparison shows a good agreement between the field-recorded PPVs and the estimated range of PPVs given by the minimum possible PPVs and the maximum possible PPVs at the monitoring points in Mandai test. The good agreement between the estimated and field-recorded values validates the proposed prediction models for estimating peak particle velocity in a rock mass with a set of joints due to application of a compressive wave at the boundary of a tunnel or a borehole.