On the relationship between silica and carbonate diagenesis in deep-sea sediments

Silica diagenesis and carbonate diagenesis are interrelated. This is confirmed by observations of DSDP Sites 462, 463, 465, 466, and 577. Carbonate sediments containing chert (1) tend to be more indurated and display more advanced diagenetic alterations, regardless of sub-bottom depth; and (2) microfossil components are more strongly affected (overgrown and/or dissolved), while the amount of micritic particles and larger, euhedral calcite crystals is greater. In addition, mass physical properties, porosity in particular, vary more widely in sediment sections containing chert. Furthermore, in the studied similarly composed sediments recrystallization of biogenic opal is indicated by a significant reduction of the specific surface area, reaching a minimum value when quartz is formed.One possible mechanism involved is the production of «surplus« dissolved carbonate created by the replacement of carbonate material by silica during the process of chert formation and silicification. The «extra« carbonate is then available for precipitation as overgrowths and cement outside the chert nodules and silicified zones. Hence silica diagenesis, if it occurs early enough in the sediment, bears some influence on carbonate diagenesis. It is therefore suggested that silica diagenesis be added to the list of factors included in the «diagenetic potential« equation ofSchlanger &Douglas (1974).

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Zusammenfassung Die Diagenese von biogenem Silikat und Karbonat steht in engem Zusammenhang, wie Beobachtungen an Sedimenten der DSDP Sites 462, 463, 465, 466 und 577 zeigen. Karbonatische Sedimente, die biogenes SiO₂ enthalten, zeichnen sich aus durch (1) größere Verfestigung und stärkere diagenetische Veränderungen — unabhängig von der Tiefe im Sediment, (2) mehr Lösung und Überwuchs an Mikrofossil-Komponenten, (3) höheren Anteil mikritischer Partikel wie auch größerer idiomorpher Kalzitkristalle, (4) stärkere Variation der sedimentphysikalischen Eigenschaften, speziell der Porosität und damit zusammenhängender Parameter.Die Umkristallisation des biogenen SiO₂ führt in ähnlich Zusammengesetzen Sedimenten zu einer drastischen Abnahme der spezifischen Oberfläche. Minimalwerte werden erreicht, wenn sich Quarz bildet.Diagenetisch wichtig ist die Produktion von zusätzlichem Karbonat durch die Silizifizierung von Karbonatschalen. Dieses »Überschuß«-Karbonat wird dann als Überwuchs, Zement oder außen an den »Hornstein«-Aggregaten gefällt. Demzufolge beeinflußt die Diagenese von biogenem SiO₂ auch die Karbonatdiagenese. Daher ist es sinnvoll, die Diagenese von biogenem SiO₂ mit zu den Faktoren zu rechnen, die das »diagenetische Potential« — wie esSchlanger &Douglas (1974) definierten — ausmachen.

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Résumé L'étude de sédiments provenant des sites DSDP 462, 463, 465, 466 et 577 montre qu'il existe une relation entre la diagenèse de la silice et celle du carbonate biogéniques. Les sédiments carbonatés qui renferment de la silice biogémque présentent: 1) une induration plus marquée et des modifications diagénétiques plus poussées — et ce indépendamment de la profondeur sous la surface du fond; 2) une dissolution et/ou un accroissement plus développés des micro-fossiles; 3) une plus grande teneur en particules micritiques et une plus grande taille des calcites idiomorphes; 4) un éventail plus large de leurs propriétés physiques, particulièrement de la porosité et des paramètres qui en dépendent.La cristallisation de l'opale biogénique, dans des sédiments de compositions semblables, se traduit par une réduction drastique de la surface spécifique, qui atteint une valeur minimale lorsque du quartz est formé.Un rôle diagénétique important est joué par l'excès de carbonate dissous engendré par la silicification de coquilles carbonatées; cet excès de carbonate est dès lors disponible pour la précipitation des auréoles d'accroissement et du ciment hors des nodules de chert et des zones silicifiées. Il s'ensuit que la diagenèse du SiO₂ biogénique influence la diagenèse du carbonate. Il conviendrait dès lors d'ajouter la diagenèse de la silice à la liste des facteurs qui interviennent dans l'équation du «potentiel diagénétique» deSchlanger etDouglas (1974).

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462, 463, 465, 466 577, . , , : 1) , ; 2) ; 3) , 4) , . SiO₂ . . . »« , , « ». , .. «, 1974 Schlanger & Douglas.

     

Calcium zoning in olivine and its relationship to silica activity and pressure

Microprobe analyses of olivine phenocrysts from nephelinite and basanite lavas show strong zoning toward calcium enrichment. Tholeiitic and other more siliceous lavas show little or no such calcium enrichment, but more extensive magnesium to iron zoning. Consideration of reactions between clinopyroxene and olivine indicate that silica activity as well as pressure is an important variable. Zoning trends toward calcium enrichment in olivine could be interpreted as a response to pressure release during crystallization. A normal, magnesium to iron, trend with no increase in calcium would, then, reflect crystallization with stable pressure conditions.     

Interaction between dissolved silica and calcium carbonate: 1. Spontaneous precipitation of calcium carbonate in the presence of dissolved silica

The kinetics of spontaneous precipitation of CaCO₃ from aqueous solution in the presence of dissolved silica was investigated by recording pH as a function of time. The presence of dissolved silica, at concentrations below saturation with respect to the amorphous phase, decreases induction time for CaCO₃ nucleation, but does not affect CaCO₃ polymorphism. For a “pure” system without silica, the surface free energy, σ, determined from classical nucleation theory is 42 mJ m⁻². This agrees well with values reported in the literature for vaterite and indicates some degree of heterogeneous nucleation, which can occur because of the relatively low degree of supersaturation used for the experiments. In the presence of 1 and 2 mM silica, σ is 37 and 34 mJ m⁻², indicating an increasing degree of heterogeneous nucleation as the amount of polymeric silica increases. The ratio of Ca²⁺ to CO₃²⁻ activity was a governing parameter for determining which CaCO₃ polymorph precipitated. At high Ca²⁺ to CO₃²⁻ activity ratios, almost all initial solid was vaterite, whereas at low ratios, a mixture of vaterite and calcite was observed. In solutions with low Ca²⁺ to CO₃²⁻ activity ratios, the presence of silica at concentrations above saturation with respect to amorphous silica led to formation of only calcite and strongly influenced the crystalline structure and morphology of the precipitates. At high Ca²⁺ to CO₃²⁻ ratios, system behaviour did not differ from that without silica.     

四川盆地碳酸盐岩中硅质特征及其对储层的影响

四川盆地碳酸盐岩储层为我国主要海相储层之一。通过分析四川盆地碳酸盐岩中硅质的宏观、微观特征,提出硅质以互层、混积、充填、交代的形式存在于碳酸盐岩中。互层硅质、充填硅质和交代硅质中二氧化硅来源以火山喷发为主,但后期沉积机制不同;混积硅质中二氧化硅来源于陆源碎屑,对物源方向具有一定的指向意义,沉积机制为陆源混积。互层硅质、充填硅质、交代硅质对储层形成具有双重意义,混积硅质对储层形成起严重破坏性作用。     

Production of carbonate and silica nano-particles in stirred bead milling

This paper presents the experimental results of the mechanical production of silica and carbonate colloidal particles below 100 nm using two types of stirred bead mills (i.e., DCP Superflow 12 and PML H/V). It is shown that the stirred bead mill with very small beads can be used as an efficient equipment for the production of the colloidal particles in nanoscale from the feed materials of several microns in sizes at high energy consumptions. The DCP Superflow mill with high power densities is superior for the effective size reduction and production rate, compared to the conventional PML H/V mill with lower power densities. The smaller particles could be produced by the DCP Superflow mill at the same level of high energy inputs as from the PML H/V mill. The “grinding limit” for the processes in the mills has been discussed.     

石笋生长直径的测定及其在古气候重建中的应用

石笋是第四纪陆地气候重建的良好信息载体,对了解过去气候和环境的演变十分重要。中国石笋具有生长相对连续,年代准确,信息丰富等特点,为全球季风及其长期演化提供了不可多得的视窗。基于石笋而开发了一系列气候替代指标,如δ18O、δ13C、微量元素及其同位素组成、有机化合物及其同位素组成、生长速率等,在石笋古气候重建中得到广泛的应用。但是,作为石笋形貌学的基本特征,对石笋的生长直径及其对气候变化的指示意义却鲜有报道。本研究中,作者首先提出一种测定石笋生长直径的方法,然后利用该方法测定了湖北清江和尚洞HS4石笋顶部35 cm的石笋生长直径,并与研究区的气温和洪涝频率记录进行比较,探讨石笋生长直径对气候变化的响应。研究表明,通过纹层的识别和不同深度上纹层宽度的测定而建立的指数回归法较好地表征了石笋的生长直径,适合于一些具有明显纹层的石笋直径测定。HS4石笋的实际生长直径比理论计算值偏小,可能与洞穴结构有关;高的落差增加了岩溶滴水的冲力,水滴飞溅而导致有效水量的损失,即滴水的有效体积减少,石笋直径偏小。与温度相比,降水对石笋直径的影响更加显著,因而石笋直径是一个有效降水的替代指标,有望在石笋古气候的研究中得到应用。      

Stable isotopes in a stalagmite from NW Sweden document environmental changes over the past 4000 years

Sundqvist, H. S., Holmgren, K., Moberg, A., Spötl, C. & Mangini, A. 2009: Stable isotopes in a stalagmite from NW Sweden document environmental changes over the past 4000 years. Boreas, 10.1111/j.1502‐3885.2009.00099.x. ISSN 0300‐9483. This study of a 4000‐year‐old stalagmite from Korallgrottan in northwestern Sweden highlights the potentials and challenges when using stable isotopes in stalagmites as climate proxies, as well as the fact that the relationship between climate and proxy may change through time. Both the oxygen and the carbon isotopes display an overall trend of enrichment together with decreasing growth rates over the time period covered by the stalagmite, which is considered a generally cooling period according to current palaeoclimate understanding. The stable isotope records show enriched isotopic values during the, for Scandinavia, comparatively cold period AD 1300–1700 and depleted values during the warmer period AD 800–1000. The indication of a negative relationship between measured δ¹⁸O and surface temperature concurs with earlier reported stalagmite records from regions with a seasonal snow cover and is further supported by the fact that the stalagmite δ¹⁸O record shows general similarities with both regional and hemispheric temperature reconstructions available for the past 500 and 2000 years, respectively. Compared with a stable isotope record of lacustrine carbonates from northern Sweden, however, shifting correlations over time between the two records indicate that a local hydrological change may have taken place at Korallgrottan, or at the lake, compared with around 1000 years ago. The earlier part of the stalagmite δ¹⁸O might thus be influenced, to some extent, by another process than the later part, which means that a negative relationship between δ¹⁸O and surface temperature might not hold for the entire 4000‐year‐old record.     

神农宫和祥龙洞洞温季节变化特征及其对石笋氧同位素组成的可能影响

通过对江西万年县神农宫和陕西宁强县祥龙洞两个洞穴内、外温度连续19个月的同步监测以了解不同时间尺度下洞穴温度变化特征。结果显示神农宫及祥龙洞洞内温度存在明显的季节性变化:（1）神农宫夏秋季洞内温度在小时-日尺度上受到降水事件的影响显著,洞内夏秋季温度波动明显高于冬春季。祥龙洞监测点所处支洞环境相对封闭,温度波动在冬春季大于夏秋季,且全年洞温变幅小于神农宫。（2）旬—季节尺度的洞温数据显示,一个完整水文年内,神农宫两个监测点SN1、SN2的温度变幅分别达到4.8 ℃和4.6 ℃,祥龙洞达到3.2 ℃。（3）两个洞穴洞内温度响应洞外气温的变化都存在滞后性,且冬春季滞后大于夏秋季,可能受深部围岩温度相对偏高、空气和围岩热导率的季节变化以及降水季节差异的影响。最后,针对洞温存在较大季节变化的洞穴讨论了不同沉积模式下洞穴温度变化对石笋氧同位素组成18O的可能影响。认为此类洞穴某一时期石笋δ18O出现较大幅度偏正或偏负不一定反映了外界气候的大幅变化,也可能仅仅是由于洞穴沉积条件发生改变而造成的。      

石笋P/Ca重建宜昌地区9 000年以来的陆地生产力

陆地生产力在全球变化,尤其是全球碳循环研究领域中,具有重要的地位。本文通过分析湖北清江和尚洞HS4石笋中P和Ca的地球化学组成,考察P/Ca对陆地生物生产力的响应。结果发现,最近50年沉积的石笋P/Ca比值与Thornthwaite Memorial生产力模型计算的区域陆地生产力具有显著的相关性,可以作为陆地古生产力的指标。以石笋P/Ca 重建的宜昌地区陆地古生产力在过去9 000年呈现波动变化的特征:8.9～6.5ka BP,陆地生产力较低;6.5～5.0ka BP,陆地生产力显著升高,并在6.4～5.6ka BP期间达到9.0ka来的最高值;5.0～4.0ka BP,处于低生产力期;4.0～1.5ka BP,生产力逐渐回升;1.5ka BP以来,生产力再次处于低值期。陆地生产力的波动明显受到全球和区域气候的制约。      

Progress in spelean stalagmite paleoclimatology and chronology

Spelean stalagmite dating using thermal ionization mass spectrometry(TIMS)on the basis of U-Th disequilibrium has contributed greatly to paleoclimatology,paleo-environment,paleo-oceanology,archaeology as well as modern volcano-magmatism studies.Results of our studies on stalagmite chronology are also reported in this paper.     

江西省滑坡与降雨的关系研究

对江西全省1973 年~2002 年间1 158个降雨型滑坡,从考虑滑坡所处地层岩性条件和坡向因素的角度,分析了江西省降雨型滑坡发生的概率与降雨的关系。从坡向因素角度分析,江西省有64 %的滑坡发生于阳坡,但降雨对于不同坡向的滑坡影响近乎相同,只是阴坡所需激发雨量和有效临界雨量较阳坡稍大3 %。6 d累计降雨量、14 d有效降雨量(有效降雨系数为0.82)、3 d累计降雨量和9 d累计降雨量分别是变质岩、岩浆岩、碳酸岩和碎屑岩类地层中发育的滑坡所对应的最相关的降雨因子。各岩类地层中发育的滑坡有80 %发生于降雨当日;岩浆岩、变质岩和碎屑岩类滑坡约12 %～14 %滞后于降雨发生,碳酸岩类滑坡有22 %滞后于降雨发生。滞后时间多为1～3 d,其中碳酸岩类滑坡滞后时间相对较短。这与降雨对不同滑体物质成分的渗透性能、岩土体强度弱化程度和速度等有关。     

The relationship of present shore platforms to past sea levels

Extant shore platforms are in process of being graded to LWL, just as the whole terrain is being so graded. Thus platforms occur at all possible heights. Other things being equal, lithology determines height. Ecology is important. On macrotidal stormy coasts (e. g. U. K.) the sea is a dominant factor. In hot humid tropics (e. g. Hawaii) intense weathering is a dominant factor (e. g. water layer weathering). Soft rocks graded to LWL have two profiles of equilibrium: (1) Ramp-type in non-soluble rocks. (2) Horizontal-type in soluble rocks. Platforms exist because the sea is more erosive above LWL than below. Endless variation exists in height of tides and waves, so the sea cannot cut at particular levels. 'Storm wave' platforms are hard rocks in exposed sites. They are flat because cut by planar swash (not waves) that returns by channels. Criteria for separating tectonic and eustatic factors are proposed.     

莺歌海盆地乐东区储层碳酸盐胶结物成因机理及与流体活动的关系

乐东A区中新统黄流组是南海北部莺歌海盆地高温超高压天然气勘探的主力层系,发育重力流水道-海底扇沉积的细、中、粗粒砂岩,中、低、特低渗物性特征,多期次、多类型碳酸盐胶结。研究碳酸盐胶结物类型、期次、成因机理及其与流体活动的关系,对于储层评价预测有重要意义。研究结果表明,碳酸盐胶结物表现为早、中、晚三期方解石与早、晚两期白云石,由早期到晚期,方解石及白云石的δ¹³C、δ¹⁸O值负偏增大,MnO、BaO、SrO等含量增高,早—中期方解石的形成与生物碎屑、碳酸盐矿物溶解再沉淀有关;晚期铁方解石、(铁)白云石的形成与深部热流体、无机CO₂、有机酸脱羧有关。方解石的溶解-沉淀受地层压力及CO₂含量共同控制,地层压力与天然气组分中CO₂含量相对较高,溶解作用较强,(铁)白云石发育;反之则溶解作用较弱,(铁)方解石发育。     

Climate variability in the SE Alps of Italy over the past 17 000 years reconstructed from a stalagmite record

Stalagmite SV1 from Grotta Savi, located at the SE margin of the European Alps (Italy), is the first Alpine speleothem that continuously spans the past c . 17kyr. Extension rate and δ¹⁸O_c record for the Lateglacial probably reflect a combination of temperature and rainfall, with rainfall exerting the dominant effect. Low speleothem calcite δ¹⁸ O_c values were recorded from c . 14.5 and 12.35 kyr, during GI-1 (Bølling— Allerød) interstadial, which in our interpretation, was warm and wet. The GS-1 (Younger Dryas) was characterized by a shift to heavier δ¹⁸ O_c, coinciding with δ¹³C_c enrichment and extremely low extension rate (<8 μm/year). These characteristics indicate that GS-1 climate was cool and dry in the SE Alps. Calibration using historical data revealed that there is a positive δ¹⁸O_c/dT relationship. A 1°C rise in mean annual temperature should correspond to c . 2.85% increase of SV-1 δc¹⁸O_c. We reconstructed a slow and steady temperature rise of c . 0.5°C since 10 kyr BP, in broad agreement with reconstructions from pollen data for SE Europe. Stalagmite SV1 indicates that climate variability in the SE Alps has been influenced by the Mediterranean Sea for the past c . 17 kyr.     

The geochemistry of carbonate diagenesis: The past,present and future

Stable carbon and oxygen isotopes (δ¹⁸O and δ¹³C values) and trace elements have been applied to the study of diagenesis of carbonate rocks for over 50 years. As valuable as these insights have been, many problems regarding the interpretation of geochemical signals within mature rocks remain. For example, while the δ¹⁸O values of carbonate rocks are dependent both upon the temperature and the δ¹⁸O value of the fluid, and additional information including trace element composition aids in interpreting such signals, direct evidence of either the temperature or the composition of the fluids is required. Such information can be obtained by analysing the δ¹⁸O value of any fluid inclusions or by measuring the temperature using a method such as the ‘clumped’ isotope technique. Such data speak directly to a large number of problems in interpreting the oxygen isotope record including the well‐known tendency for δ¹⁸O values of carbonate rocks to decrease with increasing age. Unlike the δ¹⁸O, δ¹³C values of carbonates are considered to be less influenced by diagenesis and more a reflection of primary changes in the global carbon cycle through time. However, many studies have not sufficiently emphasized the effects of diagenesis and other post‐depositional influences on the eventual carbon isotopic composition of the rock with the classic paradigm that the present is the key to the past being frequently ignored. Finally, many additional proxies are poised to contribute to the interpretation of carbonate diagenesis. Although the study of carbonate diagenesis is at an exciting point with an explosion of new proxies and methods, care should be taken to understand both old and new proxies before applying them to the ancient record.     

Uranium-series dating of pedogenic silica and carbonate, Crater Flat, Nevada

A ²³⁰Th-²³⁴U-²³⁸U dating study on pedogenic silica-carbonate clast rinds and matrix laminae from alluvium in Crater Flat, Nevada was conducted using small-sample thermal-ionization mass spectrometry (TIMS) analyses on a large suite of samples. Though the ²³²Th content of these soils is not particularly low (mostly 0.1-9 ppm), the high U content of the silica component (mostly 4-26 ppm) makes them particularly suitable for ²³⁰Th/U dating on single, 10 to 200 mg totally-digested samples using TIMS. We observed that (1) both micro- (within-rind) and macro-stratigraphic (mappable deposit) order of the ²³⁰Th/U ages were preserved in all cases; (2) back-calculated initial ²³⁴U/²³⁸U fall in a restricted range (typically 1.67±0.19), so that ²³⁴U/²³⁸U ages with errors of about 100 kyr (2σ) could be reliably determined for the oldest, 400 to 1000 ka rinds; and (3) though 13 of the samples were >350 ka, only three showed evidence for an open-system history, even though the sensitivity of such old samples to isotopic disruption is very high. An attempt to use leach-residue techniques to separate pedogenic from detrital U and Th failed, yielding corrupt ²³⁰Th/U ages. We conclude that ²³⁰Th/U ages determined from totally dissolved, multiple sub-mm size subsamples provide more reliable estimates of soil chronology than methods employing larger samples, chemical enhancement of ²³⁸U/²³²Th, or isochrons.     

Processes controlling precipitation of carbonate cement and dissolution of silica in reef and near-reef settings

Carbonate cementation in the surface layer of reefs and beachrock eliminates porosity and partially replaces detrital quartz grains. The uptake and release of CO₂ by photosynthesis and respiration in reef communities cause a shift in the carbonate buffer system of seawater. Field studies and experimentation simulating the natural settings show minimum values of CO₂ (1.9 mmoles 1^?1) and HCO₃^? (2.4 meq 1^?1) in association with maximum values of pH (9.8) and O₂ (> 100% oxygen saturation) in waters covering corals and algae prior to sunset. The converse is true for these variables prior to sunrise, when minimum values of pH (7.6) and O₂ (<66% oxygen saturation) occur with maximum values of CO₂ (2.7 mmoles 1^?1) and HCO₃^? (2.7 meq 1^?1). Experimental tanks containing plain seawater showed almost no diurnal variability in pH (a constant 7.5–7.6) or O₂ (80–90% oxygen saturation) measurements. Seawater adjacent to reef biomass, with elevated pH and supersaturated with calcium carbonate, is periodically pumped into the underlying reef and beach sediments due to pressure-buildups between the reef framework or algal zones and open waters. Carbonate precipitation and quartz dissolution follow. As the system equilibrates, pH values progressively decrease.     

An ocean-atmosphere index for ENSO and its relation to Indian monsoon rainfall

An Ocean-Atmosphere Index (OAI) for ENSO is developed using data on Southern Oscillation Index (SOI) and sea surface temperature (SST) over eastern equatorial Pacific. Seasonal values of OAI, SOI and SST have been computed for the seasons September-October-November (SON), December-January-February (DJF), March-April-May (MAM) and June-July-August (JJA). Similarly SON to DJF, DJF to MAM, MAM to JJA and JJA to SON tendencies have been worked out for SOI, SST and OAI. The relationships between Indian Monsoon Rainfall (IMR) and SOI/SST/OAI, (i) for the seasons SON, DJF and MAM before and after the monsoon and JJA concurrent with the monsoon and (ii) for SON to DJF and DJF to MAM tendencies before and after the monsoon, and MAM to JJA tendency concurrent with the monsoon have been explored. It is found that IMR is more influenced by SOI before the monsoon than it is influenced by SST before the monsoon and IMR affects SST after monsoon more strongly than it affects SOI after the monsoon. It is also observed that DJF to MAM tendencies for SOI, SST and OAI before monsoon are significantly related to IMR, among which the relationship between IMR and DJF to MAM tendency for OAI is the best.