Al speciation in tropical podzols of the upper Amazon Basin: A solid-state Al MAS and MQMAS NMR study

In the upper Amazon Basin, aluminum previously accumulated in lateritic formations is massively remobilised in soils by podzolization and exported in waters. We have investigated the speciation of aluminum in the clay-size fractions of eight horizons of waterlogged podzols lying in a depression of a plateau. The horizons illustrate the main steps involved in the podzolization of laterites. They belong to eluviated topsoil A horizons and illuviated subsoil Bhs, Bh and 2BCs horizons of weakly and better-expressed podzols located at the margin and centre of the depression. For the first time, aluminum speciation is quantitatively assessed in soils by spectroscopic methods, namely FTIR, ²⁷Al magic angle spinning (MAS) and multiple-quantum magic angle spinning (MQMAS), nuclear magnetic resonance (NMR). The results thus obtained are compared to chemical extraction data.Solid-state ²⁷Al MAS NMR spectra enable to distinguish Al bound to organic compounds from that incorporated in secondary mineral phases detected by FTIR. MQMAS experiments additionally show that both chemical shifts and quadrupolar constants are distributed for Al nuclei linked with organic compounds. Similar amounts of chelated Al are obtained from NMR spectra and chemical extractions. The study enables to highlight three major steps in the fate of aluminum. (i) Aluminum is first released by mineral weathering, feeds complexing sites of organic matter and accumulates in subsurface Bhs horizons of weakly expressed podzols (acidocomplexolysis). (ii) Complexes of aluminum with organic matter (Al-OM) then migrate downwards in sandy horizons of better-expressed podzols and accumulate at depth in less permeable 2BCs horizons. (iii) The minor amounts of aluminum present in the 2BCs horizon of the downslope podzol show that aluminum is eventually exported towards the river network, either complexed with organic matter or as Al³⁺ ions after desorption from organic compounds, due to decreasing pH or biodegradation of organic ligands. The direct spectroscopic determination of Al-speciation during the formation of podzolic soils opens new perspectives to trace metal loads in the rivers of the upper Amazon Basin.     

Origin and significance of high nickel and chromium concentrations in Pliocene lignite of the Kosovo Basin, Serbia

Trace element data from 59 Pliocene lignite cores from the lignite field in the Kosovo Basin, southern Serbia, show localized enrichment of Ni and Cr (33–304 ppm and 8–176 ppm, respectively, whole-coal basis). Concentrations of both elements decrease from the western and southern boundaries of the lignite field. Low-temperature ash and polished coal pellets of selected bench and whole-coal samples were analyzed by X-ray diffraction and scanning electron microscopy with energy-dispersive X-ray analyses. These analyses show that most of the Ni and Cr are incorporated in detrital and, to a lesser degree, in authigenic minerals. The Ni- and Cr-bearing detrital minerals include oxides, chromites, serpentine-group minerals and rare mixed-layer clays. Possible authigenic minerals include Ni---Fe sulfates and sulfides. Analyses of three lignite samples by a supercritical fluid extraction technique indicate that some (1–11%) of the Ni is organically bound. Ni- and Cr-bearing oxides, mixed-layer clays, chromites and serpentine-group minerals were also identified in weathered and fresh samples of laterite developed on serpentinized Paleozoic peridotite at the nearby Glavica and ikatovo Ni mines. These mines are located along the western and northwestern rim, respectively, of the Kosovo Basin, where Ni contents are highest. The detrital Ni- and Cr-bearing minerals identified in lignite samples from the western part of the Kosovo Basin may have been transported into the paleoswamp by rivers that drained the two Paleocene laterites. Some Ni may have been transported directly into the paleoswamp in solution or, alternatively, Ni may have been leached from detrital minerals by acidic peat water and adsorbed onto organic matter and included into authigenic mineral phases. No minable source of Ni and Cr is known in the southern part of the lignite field; however, the mineral and chemical data from the lignite and associated rocks suggest that such a source area may exist.     

洞庭盆地第四纪红土地层及古气候研究

洞庭盆地周缘广泛发育着第四纪红土地层,我们在野外对典型红土剖面进行了考察,并在岳阳市月山红土剖面进行了取样,在室内对土壤样品进行了磁化率、粘土矿物和粒度等实验分析,从而对洞庭盆地第四纪红土地层的剖面特征进行了研究,在此基础上,对洞庭盆地第四纪古气候变迁进行了探讨。月山红土剖面地层界限清晰,剖面特征明显,与中国南方其它的红土地层具有较好的地层对比性。月山红土剖面磁化率和粘土矿物分析表明:中更新世早期洞庭盆地气候干凉,中更新世晚期转为湿热;晚更新世早期气候仍保持湿热,晚更新世晚期则转为干凉;全新世以来洞庭盆地的气候再次转为湿热。粒度分析表明月山红土剖面第四纪沉积物的沉积环境为洪水盆地中的泛滥平原环境。     

Organic complexation and translocation of ferric iron in podzols of the Negro River watershed. Separation of secondary Fe species from Al species

The development of podzols in lateritic landscapes of the upper Amazon basin contributes to the exportation of organic carbon and associated metals in the black waters of the Negro River watershed. We have investigated the distribution of Fe^III in the clay-size fraction of eight organic-rich horizons of waterlogged plateau podzols, to unravel the weathering conditions and mechanisms that control its transfer to the rivers. The speciation and amount of Fe^III stored in residual mineral phases of laterites, or bound to organic compounds of weakly and well-expressed podzols, were determined by electron paramagnetic resonance spectroscopy combined with chemical analyses.Reducing conditions restrict the production of organo-Fe complexes in the subsoil B-horizons of waterlogged podzols and most of the Fe²⁺ released from the dissolution of Fe-oxides is exported to the rivers via the perched groundwater. However, significant amounts of diluted Fe^III bound to organic ligands (Fe^III_OM) and nano Fe-oxides are produced at the margin of the depression in the topsoil A horizons of weakly expressed podzols due to shorter periods of anoxia. The downward translocation of organically bound metals from topsoil A to subsoil B-horizons of podzols occurs in shorter distances for Fe than it does for Al. This separation of secondary Fe species from Al species is attributed to the physical fractionation of their organic carriers in texture contrasted B-horizons of podzols, as well as to the effect of pH on metal speciation in soil solutions and metal binding onto soil organic ligands (mostly for Al). This leads us to consider the topsoil A horizons of weakly expressed podzols, as well as the subsoil Bh horizon of better-expressed ones, as the main sources for the transfer of Fe^III_OM to the rivers. The concentration of Fe^III_OM rises from soil sources to river colloids, suggesting drastic biogeochemical changes in more oxygenated black waters of the Negro River watershed. The contribution of soil organic matter to the transfer of Fe to rivers is likely at the origin of the peculiar Fe isotope pattern recently recognized in podzolic environments.     

The natural enrichment of ferruginous weathering products and its implication for water quality in the Hunchun Basin, China

In order to evaluate the extent of a natural enrichment of Fe and Mn over the whole of the Hunchun Basin, the stability of Fe-Mn mineral phases, their status, the weathering rate of source materials, and soil characteristics were determined. A variety of samples were collected from sediments, soil profiles, and surface soils. In the solutions after a sequentially selective dissolution using sodium pyrophosphate (p), acid oxalate (o), and dithionite-citrate-bicarbonate (d), Si, Al and Fe were dominant in the d and p fractions, and Mn in the o and p fractions. The results showed that the existing phases and status of Fe and Mn were distinctly different, and that the abundance of amorphous Mn phases made thermodynamic calculation difficult. An application of these ferruginous weathering products was therefore made to understand basin development. The first terrace of the Hunchun River is more active than the second terrace, which can be inferred from it having a higher value in Fe_d/Fe_t. Amorphous Fe phases such as Fe(OH)₃ and Fe₃(OH)₈ were controlling factors of Fe in the thermodynamic calculations. The transformation of the amorphous Fe phases to more stable phases was hindered by high contents of smectite and gibbsite, amorphous opaline produced from rice roots, and organic phosphate pesticides or fertilizers in soils. Source-rock deduction using water samples suggested granitic weathering. Precipitation around the Hunchun Basin is gradually becoming more acidic. Therefore, in the future it is inevitable that ecological and environmental problems related to the Fe phases mentioned above will occur in the drinking water supply for this area, especially in that of the first terrace.     

钾盐和磷酸盐对固化土早期强度的影响研究

利用土壤板结原理,通过对硫铝酸盐水泥固化土无侧限抗压强度试验和水稳定性试验,探讨钾盐、磷酸盐对其早期强度的影响规律;通过X射线衍射（XRD）对固化土的物相成分进行了分析,探讨钾盐、磷酸盐影响固化土强度的变化内在机制。试验结果表明,钾盐、磷酸盐对固化土强度提高的阈值为0.6%,当盐掺入量低于该阈值时,固化土强度会随着盐掺量的增加而提高,当盐掺入量超过该阈值时,固化土强度会逐渐降低。盐掺入量不超过2%时,掺盐固化土水稳定性与未掺盐固化土差不多,7 d固化土软化系数基本保持在70%以上,但掺入K2SO4的固化土水稳定性较差,软化系数在60%左右。生成高强难溶具有膨胀性的矿物晶体是掺盐固化土早期强度提高的主要原因,但盐掺入量过高,固化土中矿物晶体过多膨胀作用,破坏固化土结构,而使固化土早期强度降低。     

青藏高原北部新生代构造演化在柴达木盆地中的沉积记录

青藏高原形成和演化过程中经历的构造活动,在高原的盆地中均有相应的沉积记录。柴达木盆地位于青藏高原北部,盆地新生界地层详细地记录了这些构造-沉积响应。对野外剖面和钻井岩心的新生界沉积物进行了多方面研究,其结果显示,柴达木盆地保存了青藏高原北部三个阶段的构造活动信息:①E₁₊₂的红色粗碎屑沉积物指示了始新世早期的强烈活动构造背景,沉积记录具有低ZTR指数和低重矿物稳定指数的特征,记录了全盆地范围内的造山活动和构造隆升事件,是印度-欧亚板块碰撞所致的远程响应。在这次广泛的大面积的造山活动后,区内迅速遭受剥蚀、夷平,自中-晚始新世时期起,接受沉积。因而此时柴达木盆地与可可西里盆地、乃至塔里木盆地为连通的湖盆体系。②阿尔金山前N₁和N₂1的粗碎屑沉积物记录了渐新世-早中新世阿尔金山的构造隆升事件,而柴北缘和柴西南的大范围三角洲-湖泊细粒沉积物,具有较高的重矿物稳定指数,反映了平静的构造背景,与阿尔金断裂快速走滑以及盆地总体稳定向北推移的时间相对应。大量的侧向走滑活动消减了来自印度板块的挤压应力,使得柴北缘和柴西南的沉积源区（即祁连山和东昆仑造山带）处于构造平静期。③中中新世以来全盆地向上变粗的粗碎屑沉积物,具有较低的重矿物稳定指数,记录了青藏高原北部整体强烈的地壳缩短、加厚和快速构造隆升事件。此外,综合物源分析显示,柴达木盆地新生代沉积源区性质随时间并没有发生明显的改变。     

Rare and Rare Earth Elements in Lateritized Bauxites of the Chadobets Uplift (Siberian Platform)

Doklady Earth Sciences - The mineral and chemical composition of bauxites from the Chadobets uplift of the Siberian Platform is the total product of laterites on aluminosilicate rocks (source of...     

Health care pattern and planning in Saudi Arabia

Amazonia I is a large multi-disciplinary project, now in its fourth year, concerned with the effects of changing land use on the ecology and climate of the Brazilian Amazon. It is primarily concerned with investigating the water, carbon and nutrient cycles, and brings together about 80 scientists from a number of Brasilian institutes, but especially from INPA in Manaus, CENA/USP in Piracicaba and EMBRAPA/CPATU in Belem.Major activities include the better identification of water vapour producing precipitation, to establish better water vapour circulation models (via ¹⁸O, deuterium and ³H analysis, plus radiosonding); the study of water relations of isolated forest areas; the study of various phases of the carbon cycle especially soil organic matter; primary production; and nitrogen and soil fertility studies.A first phase Regional Amazon Model (RAM) for hydrology is being developed, and it should shortly be possible to make a first research-based attempt at modelling the carbon cycle of the Amazon region.This coordinated project represents in most ways the type of research required for the International Geosphere-Biosphere Programme (IGBP) and is a major Brasilian initiative.     

Geology and engineering properties of laterites from Ilorin,Nigeria

Twelve samples of Nigerian laterites were obtained from Ilorin, a rapidly growing urban center, and capital of Kwara State, Nigeria. Three varieties of laterites (clay, gravel and crust) were identified and subjected to mineralogical, chemical and geotechnical analyses which included: identification of clay and non-clay minerals by X-ray diffraction (XRD) techniques; chemical composition by X-ray fluorescence spectrometer analysis; pH of soil in water; moisture contents and specific gravity determinations, grain size analysis; compaction test by Harvard Compaction Apparatus and unconfined compressive strength determination.The laterite soil samples are composed of kaolinite and illite clay minerals with some quartz and feldspar. They were found to be rich in SiO₂ (45%) Fe₂O₃, (16%) and Al₂0₃ (10%).These soils yielded maximum strength when compacted on the dry side of their optimum moisture content (OMC).The soils are not expected to perform very well as concrete aggregates since they contain high amounts of SiO₂ and Fe₂O₃. These oxides are known to have deleterious effects on construction materials, particularly concrete aggregates.     

Geochemical and mineralogical investigation of domestic archaeological soil features at the Tiel-Passewaaij site,The Netherlands

Archaeological soil features can be defined as areas of staining in ancient cultural soil horizons and are frequently used in surveys to locate sites and activity areas. Visual observation of these features, however, provides only limited information on their origin and the processes leading to their formation and this limits site interpretation. This paper presents the results of geochemical and mineralogical analyses of domestic archaeological soil features in order to assess their composition, formation pathway and origin. The greenish soil features studied here belong to a house plan from a Roman farmhouse located at the Tiel-Passewaaij site in the Netherlands. The soils were investigated using a range of techniques, including X-ray Fluorescence (XRF) spectroscopy, sequential soil extractions, Fourier-transformed infrared (FT-IR) spectroscopy, X-ray Diffraction (XRD) and microprobe analysis. The results indicate that the studied soil features can chemically be distinguished from off-site soils e.g. based on their phosphate and carbonate content. Mineralogical analysis of aggregate samples from soil features further reveal that quartz and feldspar minerals are coated with Ca–Fe–P phases that closely resemble anapaite and mitridatite mineral forms. The formation of these mineral phases probably resulted from periodic reductive dissolution of Fe-oxide phases and subsequent precipitation of Fe–P phases, with inclusion of Ca from anthropogenic carbonates or groundwater. The combined presence of (Ca)-carbonates, P-phases and some anthropogenic trace elements (Cu, Zn) suggests that the greenish soil features stem from manure inputs.     

Holocene fires in the northern Amazon basin

The ubiquitous occurrence of charcoal in the forest soils of the Upper Rio Negro region of Colombia and Venezuela indicates the presence of frequent and widespread fires in the Amazon Basin, possibly associated with extremely dry periods or human disturbances. Charcoal ranged from 3.12 to 24.76 mg/cm³ in the upper 50 cm of soil and was more abundant in Oxisols and Ultisols than in other soil types. Charcoal dates range from 6260 yr B.P. to the present. Several dates coincide with dry phases recorded during the Holocene. Ceramic shards were found at several sites, and thermoluminescence analysis indicates that their ages range from 3750 to 460 yr B.P. The age of charcoal and shards confirms that this region has been subjected to fire and human disturbances during the past 6000 yr.     

新生碳酸钙沉积矿物形态的影响因素分析

石笋是古气候重建的重要地质载体,文石与方解石是石笋碳酸钙晶体的常见矿物形态。根据现代洞穴监测数据分析洞穴新生碳酸钙沉积物 (Active Speleothem: AS)的矿物形态的研究较少。本文在重庆武隆芙蓉洞三个滴水点 (MP2、MP5、MP9)下放置玻璃片,收集新生碳酸钙沉积物和滴水样品,监测新生碳酸钙沉积物矿物形态、滴水的Mg/Ca比值、pH、滴率和洞穴环境等指标,分析玻璃片正面和反面新生碳酸钙沉积物的δ18O、δ13C和Mg/Ca比值。研究发现:(1) MP2滴水点下的玻璃片正反面新生碳酸钙沉积物的矿物形态均为方解石;MP5和MP9滴水点的正面沉积方解石和文石-方解石混合两种情况,反面沉积文石-方解石,且反面文石多于正面。 (2) MP2滴水Mg/Ca比值小于MP5和MP9,说明滴水Mg/Ca比值是影响新生碳酸钙沉积物矿物形态的重要因素;而滴水pH值对AS矿物形态的影响在不同滴水点有差异。(3) 不论是玻璃片正面还是反面,文石-方解石混合的新生碳酸钙沉积物δ18O和δ13C比以方解石为主的沉积物偏正,说明AS矿物形态的变化会导致δ18O和δ13C发生变化。通过在芙蓉洞的系统监测和分析,发现新生碳酸钙沉积物的矿物形态与地表环境、洞穴上部岩溶水文地质条件密切相关,并验证了洞穴新生碳酸钙沉积物的矿物形态对石笋δ18O和δ13C具有重要影响。      

吐鲁番盆地地表水和地下水主要化学成分的形成与演化

吐鲁番盆地是我国西北干旱区内陆盆地之一,盆地内赋存铁矿等重要矿产资源。研究吐鲁番盆地地表水和地下水化学成分的演化对于吐鲁番盆地地下水资源的合理开发具有重要意义。采用无机离子示踪剂的方法,通过主要离子浓度与Cl-离子浓度之间的关系,以及主要离子/Cl^- 与Cl^- 离子浓度之间的关系,对盆地地表水和地下水的主要化学成分的形成进行了分析。同时参照地表水中主要化学成分的形成与演化,揭示盆地地下水化学成分的演化过程以及盐分的潜在来源。在吐鲁番盆地,影响不同深度地下水水化学变化的主要是蒸发矿物,其来源主要包括土壤表面的蒸发矿物、土壤层和包气带中的蒸发矿物以及艾丁湖中的表层沉积物。     

Differential uplift of the Chinese Tianshan since the Cretaceous: constraints from sedimentary petrography and apatite fission-track dating

The Chinese Tianshan is one of the important international natural laboratories for studying continental geodynamics, but its uplift time, kinematics and mechanism of formation are key unresolved questions. In order to constrain the timing, kinematics and mechanism of uplift of the Chinese Tianshan, we applied sedimentary petrography and apatite fission-track dating to Cretaceous-Tertiary series from the northern Tarim Basin and the Tianshan Mountains. We collected and analyzed 79 sandstone samples and 75 detrital heavy mineral samples from the Kezilenuer-Kuqa profile (northern Tarim Basin) with a well-defined magnetostratigraphy. Our data indicate that detrital mineral maturity abruptly decreased at the disconformity between the Upper and Lower Cretaceous, and decreased again after 15(−12) Ma. The sediments in the northern Tarim Basin changed their provenance at 124 Ma, 26(−24) Ma and 15(−12) Ma, respectively. In addition, we collected and analyzed 36 primary apatite samples from the South, Central and North Tianshan. Our results show that the Chinese Tianshan underwent three phases of differential uplift. The first phase of uplift started at the southern Central Tianshan during the Early Cretaceous and propagated southward. The second phase of uplift started at the northern Central Tianshan during the Late Cretaceous and propagated also southward. The third phase of uplift started at the northern Central Tianshan during the Eocene and propagated both northward and southward. These differential uplifts have caused development of disconformity and drops in mineral maturity of detrital sediments in the northern Tarim Basin. Such a differential and heterogeneous uplift process might have been trigged by collisions of different microcontinents (i.e., Lhasa, Kohistan-Dras and India) at the southern margin of Asia. These collisions reactivated the South Tianshan Fault and then the North Tianshan Suture, and uplifted the Chinese Tianshan step by step.     

Marine muds along the Guyana coast and their origin from the Amazon basin

The mineralogical composition of clay samples from the Amazon basin and the Guyana coast, including samples collected inland and on the continental shelf, was investigated by X-ray diffraction. Also humus content, specific surface and degree of potassium fixation were determined. The muds from the Guyana coast have virtually the same composition as those of the Amazon but are very different from the Guyanese soils and river muds. This suggests that most Guyanese coastal muds come from the Amazon which is confirmed by a consideration of the quantities involved. The only measurable effect of the sea water on the mud particles moving from the Amazon to Venezuela, which takes from one month up to 1000 years, is a decrease in potassium fixation, indicating that some potassium has been taken up from the sea water. The presence of large amounts of soil chlorite in shelf samples may be due to a prolonged contact with sea water but most probably is the result of subaereal conditions during the Pleistocene.     

The impact of climate changes during the Holocene on vegetation in northern French Guiana

The impact of climatic changes that occurred during the last glacial maximum and the Holocene on vegetation changes in the Amazon Basin and the Guiana Shield are still widely debated. The aim of our study was to investigate whether major changes in vegetation (i.e. transitions between rainforests and C₄ savannas) occurred in northern French Guiana during the Holocene. We measured variations in the δ¹³C of soil organic matter at eight sites now occupied by forest or savannah. The forest sites were selected to cover two regions (forest refugia and peneplains) which are thought to have experienced different intensities of disturbance during the latest Pleistocene and the Holocene. We found that none of the forest sites underwent major disturbances during the Holocene, i.e. they were not replaced by C₄ savannahs or C₄ forest savannahs for long periods. Our results thus suggest that tropical rainforests in northern French Guiana were resilient to drier climatic conditions during the Holocene. Nevertheless, geographical and vertical variations in the ¹³C of SOM were compatible with minor changes in vegetation, variations in soil processes or in soil physical properties.     

中印度洋海盆表层沉积物稀土元素分布特征及富集规律

对中印度洋海盆14个站位的表层沉积物进行了稀土元素(REE+Y,简称REY)分布特征和富集规律研究.结果表明,样品中REY主要富集于沸石黏土和远洋黏土中(稀土元素总量最高为1239×10?6),且明显富集钇(Y)等重稀土元素(Y富集系数高达14.1,重稀土元素和Y富集系数最高为11.6);富稀土沉积物呈明显Ce亏损,发...     

The use of oxygen isotopic ratios to identify natural and anthropogenic mercury concentrations in the Lower Brazilian Pantanal

Previous studies in the Amazon Basin and the Upper Pantanal show widespread mercury contamination of fish and water as a result of gold mining, and subsequent volatilization of mercury during the recovery process. A study was initiated to assess whether atmospheric transport of mercury to the south has resulted in elevated levels in water and fish in the Lower Pantanal. Water samples were collected from streams and rivers from the Pantanal (Mato Grosso do Sul) down into the southernmost state of Brazil (Rio Grande do Sul) for total Hg concentration and oxygen isotopic analyses. Based on oxygen isotopes and conductivity, surface water samples can be considered as mixtures of three endmembers: groundwater, rain and “aged” surface water. Lowest concentrations (<2 ng/L) of total Hg were observed in the northernmost samples, especially those associated with the groundwater sources. Further south, Hg concentrations tended to increase, but higher concentrations (>2 ng/L) likely reflect direct input from more localized watershed sources. Fish collected from streams in the Pantanal had extremely low concentrations of total Hg regardless of their size or feeding habit, although one large carnivorous fish (>2 kg) had concentrations approaching 400 ng/g wet wt. All concentrations, however, were considerably lower than those observed in similar species from the region of the Amazon Basin affected by gold mining.     

Relict magnesian calcite oolite and subsidence of the Amazon shelf

Oolitic sediments occur over large portions of the outer continental shelf off northernmost Brazil and southern French Guiana. Carbon-14 dates, stable isotope values and analogies with similar deposits from other areas in the world indicate that the ooids were formed in shallow water (possibly protected hypersaline environments) during low stands of sea level. In contrast to both modern ooids and other relict ooids, however, the Amazon shelf ooids are composed entirely of magnesian calcite (12 mol % MgCO₃) and possess radial crystal microstructures. A comparison of water depths and ages of the Amazon ooids with the generally accepted eustatic sea level curve indicates that the Amazon shelf subsided more than 100 m 16-21 thousand years ago. Prior to and subsequent to the subsidence, however, the outer shelf remained relatively stable.