High-resolution measurement of Southern Ocean CO2 and O2/Ar by membrane inlet mass spectrometry

This paper evaluates the simultaneous measurement of dissolved gases (CO₂ and O₂/Ar ratios) by membrane inlet mass spectrometry (MIMS) along the 180° meridian in the Southern Ocean. The calibration of pCO₂ measurements by MIMS is reported for the first time using two independent methods of temperature correction. Multiple calibrations and method comparison exercises conducted in the Southern Ocean between New Zealand and the Ross Sea showed that the MIMS method provides pCO₂ measurements that are consistent with those obtained by standard techniques (i.e. headspace equilibrator equipped with a Li–Cor NDIR analyser). The overall MIMS accuracy compared to Li–Cor measurements was 0.8 μatm. The O₂/Ar ratio measurements were calibrated with air-equilibrated seawater standards stored at constant temperature (0 ± 1 °C). The reproducibility of the O₂/Ar standards was better than 0.07% during the 9 days of transect between New Zealand and the Ross Sea.The high frequency, real-time measurements of dissolved gases with MIMS revealed significant small-scale heterogeneity in the distribution of pCO₂ and biologically-induced O₂ supersaturation (ΔO₂/Ar). North of 65°S several prominent thermal fronts influenced CO₂ concentrations, with biological factors also contributing to local variability. In contrast, the spatial variation of pCO₂ in the Ross Sea gyre was almost entirely attributed to the biological utilization of CO_2, with only small temperature effects. This high productivity region showed a strong inverse relationship between pCO₂ and biologically-induced O₂ disequilibria (r² = 0.93). The daily sea air CO₂ flux ranged from − 0.2 mmol/m² in the Northern Sub-Antarctic Front to − 6.4 mmol/m² on the Ross Sea shelves where the maximum CO₂ influx reached values up to − 13.9 mmol/m². This suggests that the Southern Ocean water (south of 58°S) acts as a seasonal sink for atmospheric CO₂ at the time of our field study.     

60Co、137Cs在几种海洋生物中浓集问题的初步研究

本文对核电站的主要废物60Co、137Cs在几种海洋生物中的浓集和若干有关的问题进行了初步研究.     

锑原位掺杂SiO2@PDA-Sb复合材料修饰电极用于海水中Zn离子检测

本研究提出了一种用于检测海水中锌离子(Zn²⁺)含量的电化学检测方法。该方法首先应用水热法合成SiO₂@PDA-Sb复合材料,然后将该复合材料修饰到玻碳电极上制备SiO₂@PDA-Sb-Nafion/GCE,利用差分脉冲阳极溶出伏安法(DPASV)对珠江口海水水样中Zn²⁺进行测定。研究结果表明,Zn²⁺在SiO₂@PDA-Sb-Nafion/GCE上具有较强的溶出峰。在最优条件下,SiO₂@PDA-Sb-Nafion/GCE对Zn²⁺浓度在1～1 000 nmol/L范围内可实现灵敏、准确的检测,Zn²⁺的检测出限为0.71 nmol/L。加标回收率实验显示Zn²⁺加标回收率为93.19%～100.12%,表明该方法可应用于现场海水样品Zn²⁺测定。本方法具有电极制作简单、稳定性和抗干扰性良好,能够提高现有测定方法的检测限和精确度,在现场海水检测...     

Centrifuge study on the runout distance of submarine debris flows

ABSTRACT

In this paper, a series of mini-drum centrifuge experiments on motion of submarine debris flow, which are able to correctly reproduce the self-weight stresses and gravity-dependent processes, are presented. These tests were performed using artificial submarine clay with high water content, from 93 to 149%. The extremely low shear strength made the debris material behave as idealistic lubricating material when it was deposited, resulting in a linear relationship between water content and runout distance of strongly coherent debris flow. On the other hand, the dilation of the flow body and hydroplaning was observed for weakly coherent debris flow, which further increased the mobility of flow body. A densimetric Froude number Fr_d was used to indicate the threshold of hydroplaning, which occurs if the Fr_d is greater than 0.2. Finally, two simple analytical models based on prototype debris flow under 1?g condition was used to validate the experiment results, which further prove the effects of soft marine clay on the high mobility of submarine debris flow. On the other hand, when the water content exceeded 120%, the experiment results deviated from the analytical solution due to the effects of hydroplaning.     

Cu2+/SnO2复合纳米光催化剂的制备及其对海洋柴油污染物的降解

采用化学沉淀法成功制备了Cu2+/SnO2复合纳米光催化剂,采用XRD、SEM等测试手段对复合纳米光催化剂的粒径、形态等进行表征。在紫外光条件下,分别改变催化剂掺杂比、催化剂煅烧温度、催化剂投加量、柴油初始含量和光照时间等单因素,探究不同条件对Cu2+/SnO2复合纳米光催化剂降解海洋柴油污染物的影响。结果表明,自制复合纳米光催化剂可以有效降解海水中的柴油污染物,在紫外光作用下,于400℃下煅烧Cu/Sn掺杂比为0. 03的Cu2+/SnO2复合纳米光催化剂、投加量为0. 2 g/dm3、柴油初始含量为0. 15 g/dm3、H2O2溶液含量为0. 2 g/dm3、溶液的p H为7、光照时间3 h时效果最好,海水中柴油的去除率最高,达到86. 98%。Cu2+/SnO2复合纳米光催化剂用聚丙烯纳米球负载后可以实际应用于海洋中,便于回收。     

Calculation of CO2 column heights in depleted gas fields from known pre-production gas column heights

Depleted gas fields have been identified as potential targets for CO₂ storage. In order to maximise storage capacity, a target field must be deep enough to ensure that the CO₂ is in a dense phase (either liquid or supercritical). Accurate assessment of the storage capacity also requires an estimation of the amount of CO₂ that can be safely stored beneath the reservoir seal which can be estimated in several ways. In this paper we develop a methodology to convert known pre-production gas column heights into CO₂ column heights in order to estimate storage capacities. Several authors have correctly identified that the differences in interfacial tension and wettability act to reduce the threshold capillary entry pressure for CO₂ compared to natural gas, consequently reducing column height estimates. However, under reservoir conditions the density of CO₂ is substantially higher than natural gas so the buoyancy force on the seal for a fixed column height is much lower for dense phase CO₂ increasing column height estimates; we investigate the effects of this trade off on storage estimates and apply it to a typical dataset, in this case the UK North Sea.     

The influence of organics on the adsorption of copper (II) on γ-Al2O3 in seawater,model studies with EDTA

The natural “complexing capacity” of aquatic systems was determined using titration with cupric ions. It was compared with “complexing capacity” determined in the presence of both EDTA, used as a model for organic substances, and of EDTA and γ-Al₂O₃. The γ-Al₂O₃ was used as a model for solid particles of hydrous oxide in natural waters. The adsorption isotherm of copper in seawater on γ-Al₂O₃ particles was determined with and without EDTA.For EDTA alone and for the Cu—EDTA complex, it was found that they are not adsorbed on γ-Al₂O₃ in the natural seawater. However, by adsorption on solid particles, the labile ionic Cu-complex can be removed from the seawater.     

厦门湾海水中224Ra的深度分布特征及其应用

本文采用MnO₂-纤维富集、220Rn的连续射气闪烁法测定厦门湾海水中的224Ra,利用其垂直分布求出该海域的垂直涡动扩散系数(K_z),为该海域可溶性污染物扩散、迁移和海域自净能力的估算提供理论依据.该海域224Ra的垂直分布及由此得出的K_z使我们能够洞悉研究海域水体的垂直扩散特征及其时、空变化.     

Benthic remineralization and burial of biogenic SiO2, CaCO3, organic carbon, and detrital material in the Southern Ocean along a transect at 170° West

We investigated the composition, recycling, and mass accumulation rates of sediments along a transect in the Southern Ocean located from 66°S to 57°S at 170°W. This transect also corresponds to the location of a sediment trap mooring line. The sediments at the seven sites studied range from largely terrigenous material to nearly pure (>90%) biogenic silica. CaCO₃ is a minor but persistent component at most sites. Mass accumulation rates have been determined on the basis of excess ²³⁰Th in the sediments, i.e., ²³⁰Th-normalized accumulation rates. The influence of redistribution of sediments on the sea floor has been estimated from ¹⁴C analyses. The recycling of material delivered to the sediments has been characterized on the basis of pore water studies that make extensive use of both in situ sampling and shipboard extractions. The influence of the highly variable rates of input of particulate matter that characterize much of the Southern Ocean upon pore water gradients and fluxes across the sediment water interface has been considered.We find only poor correspondence between BSiO₂ burial fraction (=burial/particulate flux), a quantifiable measure of preservation efficiency, and BSiO₂ particulate rain along the transect. However, preservation does appear to be closely linked to a combination of sedimentation rate and particulate rain.The burial fraction of BSiO₂ is small relative to benthic rain (5–19%). Despite the small fraction buried, burial flux normalized to (sedimentation rate)^1/2 appears to provide a very consistent means of predicting benthic particulate rain over a large range of rain rates, including data from a number of different studies and environments. At sites with BSiO₂ rain 250 mmol m⁻² yr⁻¹ the average difference between predicted and observed rain is 25–30%. Such rain rates occur in many marine areas, particularly the Southern Ocean, with the result that this relationship potentially provides a means of estimating BSiO₂ benthic rain over prolonged periods in the past on the basis of readily measured sediment parameters.At the southern-most deep ocean station, the particulate flux was characterized by an extremely high C_org/CaCO₃ ratio (>10), but this high ratio does not appear to have a substantial influence on CaCO₃ burial. CaCO₃ is preserved in the sediments at this site despite a particulate flux with a 10-fold excess of C_org above that required for complete dissolution in the sediments. The unexpectedly high preservation of CaCO₃ is due largely to the very steep C_org oxidation rate profile at this site. As a result, a large fraction of the organic matter oxidized in the sediments does so in close proximity to the sediment–water interface where most of the metabolic CO₂ is neutralized by CO₃²⁻ from the overlying water, rather than by the dissolution of sedimentary CaCO₃.Diagenetic modeling indicates that at several of the stations, the remineralization fluxes of carbonate species across the sediment–water interface may not have been at steady state as a result of the highly pulsed nature of particulate rain in this environment. We estimate that at the time of our sampling it is possible that near-interface fluxes could have been a factor of 1.6–2 times the annual average.At every site on the transect, the burial fluxes of detrital material are substantially greater than the detrital particulate rain measured in the sediment traps, by as much as a factor of 40. Detrital burial is bimodal, being greatest at the southern and northern extremes of the transect. We postulate that the excess of burial over particulate rain in the south reflects the contribution of ice rafted debris at these high latitudes. Increases in the supply at the northern stations must have a different source. We believe that the excess at these stations is material eroded from the sea floor to the west, possibly on the Campbell Plateau, and advected by currents to the northern portion of the transect at depths below the shallow traps.     

基于ST-ConvLSTM的南海海表面CO2分压的空间和时间序列预测

海表面二氧化碳分压(pCO₂)的未来变化趋势,对统计评估全球碳收支以及理解全球气候变化背景下的海洋酸化现象至关重要。目前传统的海面pCO₂预测方法大部分基于有限的实测数据,然而实测数据存在着时间和地理方面的制约,且计算成本较高。近年来,随着时空观测数据的爆炸性增长,基于深度学习的数据驱动模型在海表面pCO₂预测方面中表现出良好的潜力。然而,由于多种环境因素与海表面pCO₂之间的关系错综复杂,到目前为止尚无十分简单有效的相关模型来对海表面pCO₂进行预测。为应对这一挑战,利用时空卷积长短时记忆神经网络(ST-ConvLSTM)模型,通过海面温度(sea surface temperature, SST)、海面盐度(sea surface salinity, SSS)、叶绿素a浓度(chl a)和海面pCO₂数据,预测南海的海面pCO₂,并将2019年1～12月的数据作为测试集对模型的表现进行了验证。结果显示, ST-ConvLSTM模型...     

基于双还原体系与膜进样质谱快速测定15N加富水样中15NO3-的方法

海洋中的氮循环是海洋生物地球化学研究的热点领域之一,而硝化过程是氮循环的关键一环,准确获取硝化速率对于丰富海洋氮循环的认识至关重要。¹⁵N标记同位素技术是目前国际上最为广泛使用的硝化速率测定方法,该方法的核心在于准确测定¹⁵N加富样品产生的¹⁵NO₂^-和¹⁵NO₃^-的含量,但目前的方法普遍存在测试时间较长、测试成本较高、所需样品体积较大或者检测限较高等问题。研究以低成本的膜进样质谱作为¹⁵N加富样品测试设备,建立了基于镉柱与氨基磺酸双还原体系测定¹⁵N加富样品中¹⁵NO₃^-含量的方法。经条件优化实验确定的具体方法:采用1 mol/L HCl配制15 mmol/L的氨基磺酸（SA）作为反应试剂除去样品原有的NO₂^-,然后利用镉柱将¹⁵NO     

Green synthesis of iron oxide (Fe3O4) nanoparticles using two selected brown seaweeds: Characterization and application for lead bioremediation

The exploitation of different plant materials for the biosynthesis of nanoparticles is considered a green technology because it does not involve any harmful chemicals. In this study, iron oxide nanoparticles (Fe₃O₄-NPs) were synthesized using a completely green biosynthetic method by reduction of ferric chloride solution using brown seaweed water extracts. The two seaweeds Padina pavonica (Linnaeus) Thivy and Sargassum acinarium (Linnaeus) Setchell 1933 were used in this study. The algae extract was used as a reductant of FeCl₃ resulting in the phytosynthesis of Fe₃O₄-NPs. The phytogenic Fe₃O₄-NPs were characterized by surface plasmon band observed close to 402 nm and 415 nm; the obtained Fe₃O₄-NPs are in the particle sizes ranged from 10 to 19.5 nm and 21.6 to 27.4 nm for P. pavonica and S. acinarium, respectively. The strong signals of iron were reported in their corresponding EDX spectra. FTIR analyses revealed that sulphated polysaccharides are the main biomolecules in the algae extracts that do dual function of reducing the FeCl₃ and stabilizing the phytogenic Fe₃O₄-NPs. The biosynthesized Fe₃O₄-NPs were entrapped in calcium alginates beads and used in Pb adsorption experiments. The biosynthesized Fe₃O₄-NPs alginate beads via P. pavonica (Linnaeus) Thivy had high capacity for bioremoval of Pb (91%) while that of S. acinarium (Linnaeus) Setchell 1933 had a capacity of (78%) after 75 min. The values of the process parameters for the maximum Pb removal efficiency by Fe₃O₄-NPs alginate beads synthesized via P. pavonica (Linnaeus) Thivy were also estimated.     

二氧化碳海洋封存的技术和研究现状

全球变暖的问题正变得日益严峻, 碳减排碳中和已成为国际社会的共识和努力目标。作为CO₂减排的重要方式之一, 二氧化碳捕集、利用与封存(Carbon Capture, Utilization and Storage, CCUS)近年来备受关注并且发展迅猛。CO₂海洋封存作为其中一种最具潜力的减排方式, 了解其发展现状对进一步研究CO₂封存具有重要的参考价值。本文介绍了CO₂海洋封存的方法和封存机理, 总结了该技术在国内外研究进展。此外, 文章还概述了我国在CO₂海洋封存上的巨大潜力和库源匹配上的优势, 以及海洋封存对环境可能造成的影响。最后, 指出推进CO₂海洋封存技术的研究并开发相应的能力, 将有助于加速推进碳减排进程、尽快实现碳中和目标。     

An overview into submarine CO2 scrubber development

An overview into the development of a carbon dioxide (CO₂) removal plant for submarines to meet the Navy's CO₂ requirements is presented.The monoethanolamine (MEA)-CO₂ removal process and parametric studies to reduce atmospheric CO₂-levels in submarines to 0.5% and possibly 0.2% are discussed.     

The Adriatic Sea M2 and K1 tides by 3D model and data assimilation

In the present work we explore the impact of assimilating local tide-gauge and altimetric data on the quality of predicting the major Adriatic tides (M₂ and K₁). To that end we compute optimal tidal open boundary conditions for a 3D high-resolution finite-element model by using an incremental assimilation formalism. The essence of the method is the use of two dynamical models where the solution in the complex 3D high-resolution model is sought via assimilation of prediction errors into the simpler 2D model with explicit inverse. In the central numerical experiment, harmonic constants from 12 tide gauges are assimilated and the results are analysed at 31 locations, hence 19 independent ones. The data assimilation contributes to the reduction of maximum amplitude error from 5.6 to 0.5 cm for M₂ and from 3.9 to 0.1 cm for K₁. The assimilation procedure is repeated by assimilating suitably processed Topex/Poseidon altimeter data, again validating the outcome at 31 tide gauge locations. The result was very similar to the gauge-data assimilation outcome. The model output is also validated with the current data, not used in the assimilation. At two locations and at three depths the model was able to reproduce the major and the minor semi-axes of tidal ellipses, as well as their orientations very well.     

The influence of macronitrogen (NO3- and NH4+) addition with Ulva pertusa on dissolved inorganic carbon system

The influence of macronitrogen (NO - 3 and NH + 4 ) addition with Ulva pertusa on dissolved inorganic carbon system in seawater was studied. The results indicate that p(CO 2 ) and HCO 3 concentration decrease significantly, while pH and CO 2- 3 concentration increase significantly. When the concentration of NO 3 was less than 71 μmol/dm 3 or NH + 4 was less than 49.7 μmol/dm 3 , dissolved inorganic carbon (DIC) absorption rates by Ulva pertusa generally increased with the increasing of nitrogen concentration. The DIC decreased 151 μmol/dm 3 with the addition of 71 μmol/dm 3 NO 3 and decreased 232 μmol/dm 3 with the addition of 49.7 μmol/dm 3 NH + 4 after the experiment compared with DIC measured without nitrogen addition. A significant negative-correlation was found between c(DIC) and growth rate (μ) of Ulva pertusa (r = -0.91, P <0.000 1, n=11). NH + 4 had more influence on the species of inorganic carbon system than NO 3 .     

可口革囊星虫(Phascolosoma esculenta)重组铁蛋白富集Pb2+等重金属特性和功能研究

利用可口革囊星虫重组铁蛋白富集Pb²⁺、Fe³⁺、Cd²⁺、Cr³⁺、Cu²⁺、Mn²⁺、Sn²⁺和Zn²⁺等8 种重金属离子后, 通过透射显微镜和傅里叶红外光谱测定蛋白的超微结构变化和内部基团特性。以 天然的马脾铁蛋白为对照, 观察重组铁蛋白与天然铁蛋白的差别。结果显示, 重组铁蛋白富集Pb²⁺ 和其它7 种重金属离子后蛋白体积大小与重金属离子种类直接相关。重组铁蛋白相对天然铁蛋白来 说在富集不同种类重金属离子后, 除了非特异性酰胺特征峰和蛋白特征峰外, 还出现一些专门富集 某些重金属离子的特异基团, 如:-CH₃、-CH₂-、-CH-、-NH-、-SO₃-、-COOH、-S=S-和-C-S-C 等。 通过细胞实验进一步验证了铁结合蛋白能够通过富集重金属离子Pb²⁺来保护小鼠成骨前体细胞 MRC3T3-E1, 使细胞的死亡率明显降低(P<0.05).     

Accurate measurement of O2, N2, and Ar gases in water and the solubility of N2

The degree of atmospheric saturation for O₂, Ar, and N₂ gases in water can be determined to accuracies of ±0.1–0.3% using mass spectrometry to determine the gas ratios and Winkler titrations for oxygen analysis. We describe methods used to obtain this level of accuracy and precision. Oxygen accuracy of ±0.1% can be obtained by careful attention to standardization using KIO₃ standards that have been corrected for impurities. Accurate O₂/Ar and O₂/N₂ gas ratios (±0.1–0.2%) are obtainable by measuring the mass ratios against the atmosphere if the effect of different gas concentrations on the performance of the mass spectrometer are taken into account. Oxygen and argon saturation values have been determined previously to accuracies of less than or equal to ±0.1%, but published estimates of the saturation value for nitrogen differ by more than 1%. We have redetermined the N₂ saturation value at 19°C and zero salinity to be 0.92% greater than the results reported in the work of Weiss (1970).     

2015年9月16日智利Mw 8.3级地震:海啸波从近场到远场的特征分析

On September 16, 2015, an earthquake with magnitude of M_w 8.3 occurred 46 km offshore from Illapel, Chile,generating a 4.4-m local tsunami measured at Coquimbo. In this study, the characteristics of tsunami are presented by a combination of analysis of observations and numerical simulation based on sources of USGS and NOAA. The records of 16 DART buoys in deep water, ten tidal gauges along coasts of near-field, and ten coastal gauges in the far-field are studied by applying Fourier analyses. The numerical simulation based on nonlinear shallow water equations and nested grids is carried out to provide overall tsunami propagation scenarios, and the results match well with the observations in deep water and but not well in coasts closed to the epicenter. Due to the short distance to the epicenter and the shelf resonance of southern Peru and Chile, the maximum amplitude ranged from 0.1 m to 2 m, except for Coquimbo. In deep water, the maximum amplitude of buoys decayed from9.8 cm to 0.8 cm, suggesting a centimeter-scale Pacific-wide tsunami, while the governing period was 13–17 min and 32 min. Whereas in the far-field coastal region, the tsunami wave amplified to be around 0.2 m to 0.8 m,mostly as a result of run-up effect and resonance from coast reflection. Although the tsunami was relatively moderate in deep water, it still produced non-negligible tsunami hazards in local region and the coasts of farfield.     

Complexation of zinc by exudates from Skeletonema costatum grown in culture

Measurements have been made, by amperometric titration using anodic stripping voltammetry, of the zinc binding properties of organic material released by Skeletonema costatum in culture, after the stationary growth phase had been reached. Titration curves showed two inflection points, interpreted as indicating the presence of two analytically distinguishable ligand assemblages (L₁ and L₂). The complexing capacities of these assemblages increased with time and the associated conditional stability constants K₁^′ and K₂^′ decreased with time. This apparent reduction in stability constants could be accounted for by complex dissociation. Several methods for the calculation of complexing capacity and stability constant were employed and although the calculated concentrations of C_L varied, each method showed similar trends.Size fractionation of the organic moieties revealed that C_L, was composed of organic assemblages with apparent molecular weight greater than 3 × 10⁴. The ligands L₂ were of mixed size composition.