The control of Phanerozoic atmosphere and seawater composition by basalt–seawater exchange reactions

We present results from a long term geochemical cycling model, with a focus on the sensitivity of atmospheric carbon dioxide, oxygen, and the major element composition of seawater to seafloor spreading rates. This model incorporates rock weathering, basalt–seawater exchange reactions, and the formation and destruction of chemical sediments and organic matter. Hydrothermal reactions between seafloor and seawater involving calcium, magnesium, sodium, potassium, sulfate and carbon are the high temperature counterparts to low temperature redox, weathering, precipitation and diagenetic reactions. A major source of uncertainty is the extent to which these exchange fluxes are controlled by seafloor spreading rate. In addition, the return fluxes of these components to the atmospheric and primary silicate reservoirs reflect not only the overall rates of subduction and metamorphism, but the distribution of the overlying sedimentary burden and authigenic minerals formed during basalt alteration as well. In particular, we show how the stoichiometry of exchange fluxes (Mg/Ca and SO₄/Ca) may buffer atmospheric CO₂ and O₂ concentrations.     

Time and the crystallization of apatite in seawater

Carbonate fluorapatite has been synthesized in seawater in an experiment of nearly 10-years duration. The addition of phosphate to seawater whose fluoride concentration had been increased to 7.6 mg/l brought about an initial amorphous phosphate precipitate. After 20 months, a crystalline magnesium phosphate phase developed within the amorphous phosphate. Crystallization of apatite, which occurred during the last 3 years of the experiment, was accompanied by dissolution of the crystalline magnesium phosphate phase.The MgO content of the apatite (1.9 percent) is high in comparison to Tertiary and older apatite but similar to some young apatite; the CO₂ content (3.6 percent) is medium, and the fluorine content (2.2 percent) is low but again similar to some young apatite. The hydroxyl ion (OH^?) likely fills the need for additional fluorine-position atoms. The mole ratio of Ca plus substituent elements to P plus substituent elements (1.50) is low in comparison to the expected ratio of 1.67. The substitution of the hydronium ion (H₃O⁺) for Ca may account for this difference.The synthesis of apatite in seawater demonstrates that the factor of time overcomes the well known inhibiting effect of magnesium upon the crystallization of apatite. It also implies that given an adequate supply of phosphate, apatite can form in most ocean environments and likely plays a major pan in the control of the phosphate content of seawater.     

Changes in the poleward energy flux by the atmosphere and ocean as a possible cause for ice ages

It is proposed that the two preferred modes of temperature and circulation of the atmosphere which occurred over the past 100,000 yr correspond to two modes of partitioning of the poleward energy flux between the atmosphere and ocean. At present the ocean carries an appreciable fraction of the transport, for example about three-eighths at 30°N. In the cold mode it is suggested that the ocean carries less, and the atmosphere more, than at present. During the formation of the ice, at 50,000 BP, for example, the overall flux is expected to be slightly lower than at present and during melting, at 16,000 BP, slightly higher. The transition between the modes is seen as a natural imbalance in the atmosphere-ocean energy budget with a gradual warming of the ocean during an Ice Age eventually cluminating in its termination. At the present the imbalance is thought to correspond to a natural cooling of the ocean, which will lead to the next Ice Age.The magnitude of temperature changes in the polar regions differ between the hemispheres in the same way as present seasonal changes, being larger in the northern than in the southern hemisphere.Overall the atmospheric energy cycle was more intense during the Ice Ages than now.Observational tests are proposed by which predictions from the present arguments may be compared with deductions about the environment of the past.Data used for the present state of the atmospheric general circulation are the latest global data available and contain no known major uncertainties. However, data for the oceanic circulation and energy budget are less well known for the present and almost unknown for the past. Hence the proposed imbalances must be treated as part of a speculative hypothesis, but one which eventually may be subject to observational test as no solar variability is invoked.     

Mercury exchange between the atmosphere and low mercury containing substrates

Mercury is emitted to the air from Hg-enriched and low Hg-containing (natural background) substrates. Emitted Hg can be geogenic, or can be derived from the re-emission of Hg that was previously deposited to the soil from the atmosphere. Atmospheric Hg can be derived from natural and/or anthropogenic sources and can be deposited by wet or dry processes. It is important to understand the relative magnitude of emission, deposition, and re-emission of Hg associated with terrestrial ecosystems with natural background soil Hg concentrations because these landscapes cover large terrestrial surface areas. This information is also important for developing biogeochemical mass balances, assessing the impacts of atmospheric Hg sources, and predicting the effectiveness of regulatory controls at local, regional, and global scales.The major focus of this paper is to discuss air–substrate Hg exchange for low Hg-containing soils (<0.1 μg Hg g⁻¹) from two areas in Nevada and one in Oklahoma, USA. Data collected with field and laboratory gas exchange systems are presented. Results indicate that in order to adequately characterize substrate–air Hg exchange, diel and seasonal data must be collected under a variety of environmental conditions. Field and laboratory data showed that dry deposition of gaseous Hg to substrates with low Hg concentrations is an important process. Environmental parameters important in influencing emissions include soil water content, incident light, temperature, atmospheric oxidants, and air Hg concentrations. There are synergistic and antagonistic effects between these parameters complicating prediction of flux.     

潮间带滩涂沉积物与水体热通量模拟

为了揭示滩涂对近岸水温影响,开展潮间带滩涂沉积物与海水之间热量交换研究。以韩国西南海岸的滩涂为例,建立滩涂沉积物温度模型,模拟不同潮汐状态下沉积物垂向剖面温度以及沉积物与水体间的热通量,并分析了季节、滩涂位置、潮位-太阳辐射相位对热通量的影响。研究表明:模拟出的沉积物温度与实测值吻合较好。沉积物与水体存在大量热量交换,且集中在淹没后的前3 h,最大热通量可达398.7 W/m2。冬季月份海水向滩涂净传热。夏季月份滩涂向水体净传热,且当滩涂淹没时刻发生在当地正午或正午过后3 h内,滩涂传递给水体的热量相对较大,达2.0 MJ/（m2·d）;累积热通量随滩涂干滩率的减小而减小。研究成果为进一步深入研究滩涂影响下近岸水温变化提供了技术支撑。     

Advances in microwave remote sensing of the ocean and atmosphere

This article reviews the current state-of-the-art and future prospects of the microwave techniques for remote sensing of the earth’s atmosphere and ocean. Geophysical parameters and their relationship with measured thermal microwave radiation is established through radiative transfer processes. The atmospheric temperature profile obtained from microwave sounding unit (msu) onboardtiros-N series of satellites is operational and is used for numerical weather prediction. The demonstrated applications of scanning multichannel microwave radiometer (smmr) onboard most recent and advancedseasat satellite are highlighted.The capability ofseasat active sensors for monitoring ocean parameters have also been indicated. Feasible applications of microwave techniquese.g. moisture profile with advanced moisture sounder (amsu), and surface pressure from multifrequency active microwave pressure sounder (mps) are also described. Finally the recent and advanced microwave limb sounding (mls) technique and its applications to upper atmospheric research has been reviewed.     

不同补给条件下裂隙-管道介质间水流交换的示踪试验研究

为探究岩溶含水系统中裂隙-管道介质间不同补给方式下水流交换情况,在实验室内借助高精度摄像仪和有色示踪剂对其进行可视化观测。设计多组试验对单独补给裂隙、共同补给、裂隙和落水洞分开同时补给三种补给方式下水流交换情况进行探讨,从而定性地分析水流交换情况。试验结果表明:落水洞对裂隙水扩散的影响随裂隙距离落水洞的距离增大而减小;相较于共同补给情况,单独补给裂隙情况下落水洞对裂隙水扩散影响较大;在分开同时补给情况下裂隙与落水洞补给水量相同时,仅呈现裂隙对落水洞的单向补给。     

Estimating the carbon transfer between the ocean, atmosphere and the terrestrial biosphere since the last glacial maximum

Carbon dioxide records from polar ice cores and marine ocean sediments indicate that the last glacial maximum (LGM) atmosphere CO₂ content was 80–90 ppm lower than the mid-Holocene. This represents a transfer of over 160 GtC into the atmosphere since the LGM. Palaeovegetation studies suggest that up to 1350 GtC was transferred from the oceans to the terrestrial biosphere at the end of the last glacial. Evidence from carbon isotopes in deep sea sediments, however, indicates a smaller shift of between 400 and 700 GtC. To understand the functioning of the carbon cycle this apparent discrepancy needs to be resolved. Thus, older data have been reassessed, new data provided and the potential errors of both methods estimated. New estimates of the expansion of terrestrial biomass between the LGM and mid-Holocene are 700 GtC ± > 300 GtC, using the ocean carbon isotope-based method, compared with of 1100 GtC ± > 500 GtC using the palaeovegetation estimate. If these estimates of the carbon shift to the terrestrial biosphere are equilibrated with the dissolved carbon in the oceans, and the CaCO₃ compensation of the ocean is taken into account, then the glacial atmospheric CO₂ would have been between 50 (± 30) ppm and 95 (± 50) ppm higher. The glacial atmosphere therefore should have had a CO₂ partial pressure of between 330 and 375 μatm. Hence, a rise of between 130 and 175 μatm in atmospheric CO₂, rather than 80 μatm, at the end of the last glacial must be accounted for.     

Factors controlling the solubility of aerosol trace metals in the atmosphere and on mixing into seawater

Previous work has shown that the type and pH history of an aerosol governs trace metal solubility in rainwater. This study concentrates on the crustal elements Al, Fe and Mn and identifies additional processes which affect dissolution not only in the atmosphere but also on mixing into seawater. Aerosol dissolution experiments (at aerosol concentrations of about 30 mg 1^–1) show manganese exhibiting high solubility at the low pH values typical of clouds (54±2.5% at pH 2, with results expressed in mole percent units) with 85% of this increase occurring within 6 hours of acidification. The percentage dissolution decreases to 50% at pH values representative of rainwater (pH 5.5) and to 26±4% at pH 8, typical of seawater. No such dramatic solution phase removal occurs at pH 8 in the presence of inorganic anions (to a final solubility of 44±2%). Thus the extent of manganese dissolution depends strongly on whether aerosols are cycled through acidic environments and on subsequent inorganic complexation once rainwater mixes into sea. Aluminium shows highest dissolution (7.1±0.6%) at low pH with 78% of this increase occurring within 6 hours of acidification. Rapid solution phase removal occurs on increasing the pH to that representative of rainwater (to 0.9±0.4% with 87% of this decrease occurring within 15 min). As a consequence of acid cycling and aluminium's amphoteric nature, solubility is enhanced at seawater pH (2.3±0.3%) over that in rain. Iron shows a strong pH-solubility relationship with highest solubility at low pH (4.7±0.2%), 70% of this value being reached within 6 hours of acidification, and decreasing rapidly to 0.17% as pH is raised to 8. Addition of inorganic anions at pH 8 to simulate mixing into seawater causes a further decrease in solubility, perhaps due to anion induced colloid destabilisation. Photochemical reduction also effects solubility under low pH conditions with Fe(II) comprising 1% of the total iron in the Saharan Aerosol used and 8.4% in an Urban material at a pH of 2. This element shows rapid solution phase removal with increasing particulate load which is tentatively rationalised in terms of a simple Kd approach.     

Hydrothermal systems of the hadean ocean and their influence on the matter balance in the crust-hydrosphere-atmosphere system of the early earth

This paper reports the first results of kinetic and thermodynamic modeling of interaction between the komatiitic material of the earliest terrestrial ocean and seawater. The modeling was aimed at reconstructing geochemical effects accompanying the early evolution of the earth’s outer shells, atmosphere, and hydro-sphere. We also explored the character of mineral transformations in the protooceanic crust during its hydro-thermal alteration. Kinetic and thermodynamic simulation by means of the GEOCHEQ program complex was the main tool of our study. The results of modeling allowed us to estimate the character of the environment and the duration of the formation of the oldest banded iron formation (BIF) and volcanogenic massive sulfide (VMS) deposits and reconstruct main trends in the compositional variations in the hydrosphere and atmosphere that coexisted with them.     

黄土裂隙的漫灌效应对斜坡稳定性的影响分析

以甘肃省黑方台地区滑坡为研究对象,在非饱和土特性试验基础上,根据地下水位的监测资料建立典型斜坡饱和-非饱和渗流模型,模拟斜坡灌溉作用后裂隙对斜坡渗流场的影响,研究斜坡裂隙效应对斜坡稳定性的影响。结果表明:灌溉水迅速沿裂隙下渗,形成渗流优势通道;裂隙附近土体的孔隙水压力迅速升高,导致其局部形成饱和区域;随着裂隙数量的增加,饱和区域明显增大,且裂隙的位置越靠近台塬边缘,对斜坡边缘的孔隙水压力及基质吸力影响越显著。综合斜坡稳定性分析结果可知:裂隙发育位置越靠近台塬边缘,斜坡稳定性越差;而裂隙数量的增加对于斜坡的稳定性影响更大,且裂隙对于斜坡稳定性的影响是一个短时间过程。夯填裂缝是控制滑坡发生的有效途径。     

烟台市海水入侵程度及影响因素探讨

介绍了烟台市开发区夹河地区20年来海水入侵的现状及过程。基于区内4个监测井点的长期观测资料,讨论了影响海水入侵程度的主要因素,认为烟台市海水入侵程度与区内地下水动态关联密切。在海侵区内,地下水被海水浸染的程度主要受地下水位降深控制,地下水降落漏斗范围内海水对地下水浸染程度随水位下降逐年加剧,而漏斗区外地下水质则多年保持相对稳定。     

根系和裂隙对土体水力和力学特性影响数值模拟

为探究根系和裂隙对土体水力及力学特性的影响,利用有限元软件计算降雨过程中裂隙和根土间隙对渗流场的影响,并以渗流计算结果为基础,分析降雨对根系固土作用的影响,采用分区强度折减法对降雨前后根?土复合体进行直剪试验模拟,同时考虑了侧根倾角的影响。结果表明,裂隙和根土间隙为雨水入渗提供优先通道,降雨影响深度随裂隙深度增加而增加;有根系时降雨影响深度由主根深度决定,侧根倾角对其影响较小,考虑根土间隙影响的降雨影响深度相较于无根系工况增加了93.3%;根系能显著提高土体的抗剪强度,相对于垂直主根方向的不同倾角,侧根增加土体抗剪强度由大至小依次为60o、45o、30o侧根和无根系;雨水入渗降低了土体强度,同时削弱了根系固土作用,使得降雨后根-土复合体抗剪强度大幅降低,是许多植被覆盖边坡仍发生浅层滑动原因之一。     

Major cation gradients in DSDP interstitial waters: the role of diffusive exchange between seawater and upper oceanic crust

Interstitial water analyses from DSDP Legs 1–53 were surveyed to identify sites at which the dominant process supporting gradients of major seawater cations is alteration of the underlying oceanic crust. Sites with thin sediment cover are generally without gradients: sites with appreciable sediment accumulation are generally with gradients. The transition is probably the result of cessation of convective circulation within the sediments. A model is developed for the diffusive flux through an accumulating, unreactive sedimentary layer supported by continued reaction within the crust. The model is consistent with the observations provided that convection within the crust extends to depths > 1 km and that convective flow within the sediments ends once 100–150 m of sediment accumulates. The model suggests a steady state gradient inversely proportional to the sedimentation rate: this dependence is apparent in the data, however, some variation in the reaction rate is also required. Fluxes of Mg and Na are systematically related to the flux of Ca which because of its mobility serves as a tracer of hydrolysis of the basalt. When the Ca flux is low, the Mg flux serves as the principal sink for alkalinity produced during basalt hydrolysis. When the Ca flux is high, the Mg flux becomes diffusion-limited and Nabearing alteration phases must form. The fluxes resulting from these alteration reactions exert little influence on either the chemistry of seawater or that of the upper crust.     

Enhancement and inhibition of iron photoreduction by individual ligands in open ocean seawater

In laboratory experiments, we investigated the effect of five individual Fe-binding ligands: phaeophytin, ferrichrome, desferrioxamine B (DFOB), inositol hexaphosphate (phytic acid), and protoporphyrin IX (PPIX) on the Fe(II) photoproduction using seawater of the open Southern Ocean. Addition of 10-100 nM Fe(III) to open Southern Ocean seawater without the model ligands and containing; 1.1 nM dissolved Fe(III), 1.75 ± 0.28 equivalents of nM Fe of natural ligands with a conditional stability constant (log K′) of 21.75 ± 0.34 and a concentration DOC of 86.8 ± 1.13 μM C leads to the formation of amorphous Fe(III) hydroxides. These amorphous Fe(III) hydroxides are the major source for the photoproduction of Fe(II). The addition of the model ligands changed the Fe(II) photoproduction considerably and in various ways. Phaeophytin showed higher Fe(II) photoproduction than ferrichrome and the control, i.e., amorphous Fe(III) hydroxides. Additions of phytic acid between 65 and 105 nM increased the concentration of photoproduced Fe(II) with 0.16 nM Fe(II) per nM phytic acid, presumably due to the co-aggregation of Fe(III) and phytic acid leading via an increasing colloidal surface to an increasing photoreducible Fe(III) fraction. DFOB and PPIX strongly decreased the photoproduced Fe(II) concentration. The low Fe(II) photoproduction with DFOB confirmed reported observations that Fe(III) complexed to DFOB is photo-stable. The PPIX hardly binds Fe(III) in the open Southern Ocean seawater but decreased the photoproduced Fe(II) concentration by complexing the Fe(II) with a binding rate constant of k_Fe(II)PPIX = 1.04 × 10⁻⁴ ± 1.53 × 10⁻⁵ s⁻¹ nM⁻¹ PPIX. Subsequently, PPIX is suggested to act as a photosensitizing producer of superoxide, thus increasing the dark reduction of Fe(III) to Fe(II). Our research shows that the photochemistry of Fe(III) and the resulting photoproduced Fe(II) concentration is strongly depending on the identity of the Fe-binding organic ligands and that a translation to natural conditions is not possible without further characterization of the natural occurring ligands.