Effects of temperature on silicate weathering: Solute fluxes and chemical weathering in a temperate rain forest watershed,Jamieson Creek,British Columbia

Chemical weathering of silicate minerals has long been known as a sink for atmospheric CO₂, and feedbacks between weathering and climate are believed to affect global climate. While warmer temperatures are believed to increase rates of weathering, weathering in cool climates can be accelerated by increased mineral exposure due to mechanical weathering by ice. In this study, chemical weathering of silicate minerals is investigated in a small temperate watershed. The Jamieson Creek watershed is covered by mature coniferous forest and receives high annual precipitation (4000 mm), mostly in the form of rainfall, and is underlain by quartz diorite bedrock and glacial till. Analysis of pore water concentration gradients indicates that weathering in hydraulically unsaturated ablation till is dominated by dissolution of plagioclase and hornblende. However, a watershed scale solute mass balance indicates high relative fluxes of K and Ca, indicating preferential leaching of these solutes possibly from the relatively unweathered lodgement till. Weathering rates for plagioclase and hornblende calculated from a watershed scale solute mass balance are similar in magnitude to rates determined using pore water concentration gradients.When compared to the Rio Icacos basin in Puerto Rico, a pristine tropical watershed with similar annual precipitation and bedrock, but with dissimilar regolith properties, fluxes of weathering products in stream discharge from the warmer site are 1.8 to 16.2-fold higher, respectively, and regolith profile-averaged plagioclase weathering rates are 3.8 to 9.0-fold higher. This suggests that the Arrhenius effect, which predicts a 3.5- to 9-fold increase in the dissolution rate of plagioclase as temperature is increased from 3.4° to 22 °C, may explain the greater weathering fluxes and rates at the Rio Icacos site. However, more modest differences in K and Ca fluxes between the two sites are attributed to accelerated leaching of those solutes from glacial till at Jamieson Creek. Our findings suggest that under conditions of high rainfall and favorable topography, weathering rates of silicate minerals in warm tropical systems will tend to be higher than in cool temperate systems, even if the temperate system is has been perturbed by an episode of glaciation that deposits regolith high in fresh mineral surface area.     

The dissolution kinetics of atacamite in the acid range and the stability of atacamite containing soils from Namaqualand,South Africa

The Cu hydroxy mineral, atacamite, is commonly associated with saline environments and is generally thought to dissolve rapidly in the presence of fresh water. A Cu contaminated soil from the arid Namaqualand region, South Africa, shows atacamite as the dominant Cu containing mineral. The stability of the Cu phase in this soil was determined through equilibrium and leaching studies using both deionised water (DI) and a concentrated (0.5 M) NaCl solution. Initially a high concentration of exchangeable Cu was released from the soils leached with NaCl. Continued leaching with NaCl resulted in a substantial decrease in Cu release as atacamite equilibria started to control dissolved Cu. This suggests that an initial spike of Cu laden water will leach from the soils at the onset of a large rainfall event. Further additions of water will result in a lower but sustained release of Cu from the soil. The Cu contaminated soils are exposed to acidic sulphate leachate thus the dissolution kinetics of synthetic atacamite in the acidic range (pH 5.5–4.0) was determined in both NaCl and DI solutions. The kinetic data showed that atacamite dissolution rates are significantly higher in DI than in NaCl but the rates converge at pH 4. In comparison to common acid soluble minerals, atacamite displays a moderate dissolution rate (10^−9.55–10^−7.14 mol m⁻² s⁻¹) within the acid range (pH 5.5–4.0). The atacamite dissolution reaction order with respect to pH is 1.3 and 1.6 in DI and NaCl solutions, respectively, suggesting that dissolution rates of atacamite are highly pH dependent in the acid range. The type of acid used to lower the pH had no effect on the reaction kinetics, with HNO₃ and H₂SO₄ resulting in comparable dissolution rates of atacamite at pH 4.5.     

The influence of mineralogy on weathering rates and processes in an acid-sensitive granitic catchment

Weathering in an upland catchment on granitic parent material has been studied by chemical and mineralogical analyses of soils. Long-term weathering rates for base cations, calculated from chemical analyses of the mineral horizons from soil profiles using Zr as an internal, immobile, index element, are among the smallest recorded for Scottish soils (1.7–3.1 meq m⁻² a⁻¹), indicating that these soils are susceptible to acid deposition. Sodium is the base cation lost to the greatest extent from the soils, due to weathering of plagioclase feldspar, mainly in the coarse size-fractions. Calcium is lost not only from plagioclase feldspar, but also from hornblende, grains of which show dissolution etch pits and denticulate surface features when examined by scanning electron microscopy. Weathering of hornblende, present in basic inclusions in the granite, is a significant weathering process in these soils. A range of values for ⁸⁷Sr/⁸⁶Sr ratios in stream-waters confirms the spatial variability of the material supplying Ca to the streams. The current weathering rate, calculated from input–output budgets to be 28.9 meq m⁻² a⁻¹, is much greater than the long-term weathering rate, but small compared to other catchments on similar parent material.     

Impact of nitrogenous fertiliser-induced proton release on cultivated soils with contrasting carbonate contents: A column experiment

An experimental study was carried out in order to evaluate the impact of nitrogen fertiliser-induced acidification in carbonated soils. Undisturbed soil columns containing different carbonate content were sampled in the field. Fertiliser spreading was simulated by NH₄Cl addition on top of the soil column. Soil solution composition (mainly nitrate and base cations) was studied at the soil column’s base. Nitrification occurred to a different extent depending on soil type. Higher nitrification rates were observed in calcareous soils. In all the soil types, strong correlations between leached base cation and nitrate concentrations were observed. Regression coefficients between base cations, nitrate and chloride were used to determine the dominant processes occurring following NH₄Cl spreading. In non-carbonated soils, nitrogen nitrification induced base cation leaching and soil acidification. In carbonated soils, no change of soil pH was observed. However, fertilisers induced a huge cation leaching. Carbonate mineral weathering led to the release of base cations, which replenished the soil exchangeable complex. Carbonated mineral weathering buffered acidification. Since direct weathering might have occurred without atmospheric CO₂ consumption, the use of nitrogen fertiliser on carbonated soil induces a change in the cation and carbon budgets. When the results of these experiments are extrapolated on a global scale to the surface of fertilised areas lying on carbonate, carbonated reactions with N fertilisers would imply an additional flux of 5.7 × 10¹² mol yr⁻¹ of Ca + Mg. The modifications of weathering reactions in cultivated catchments and the ability of nitrogen fertilisers to significantly modify the CO₂ budget should be included in carbon global cycle assessment.     

Impact of trace mineral phases on the total solute flux from andesitic volcanics

Recent work on the weathering of high standing islands (HSI’s) of New Zealand (Goldsmith et al., 2008), Dominica (Goldsmith et al., 2010) Martinique and Guadeloupe (Rad et al., 2006) and portions of the Philippines (Schopka et al., 2011) shows weathering rates based on stream water chemistry for areas draining andesitic terrains are comparable to weathering rates determined for basaltic terrains, indicating that andesite weathering might be much more important in drawing down atmospheric CO₂ than previously recognized. While an easily erodible parent material has been largely attributed to sustaining rates at these locations, little is known to known regarding its associated reaction kinetics. We conducted a series of batch dissolution experiments on andesitic material collected from ∼10,000 year old tephra deposits from Dominica to determine the dissolution rate of major and trace mineral phases to better understand geochemical processes controlling weathering flux from these areas. Dissolution experiments were conducted over a range of pH (4 and 7) on bulk samples and mineral separates.The dissolution rates based on Si release from the Dominica tephra bulk samples were similar, and ranged from 0.04 to 0.13 μmole Si/g-day in water, and ∼0.14 to 0.27 μmole Si/g-day in dilute acid (initial pH ∼4). Although the bulk of the ash is predominately composed of vesicular felsic (Na–Al–Si) volcanic glass, reaction rates and stoichiometry indicate ash dissolution is dominated by the reactivity of trace Mg or Ca-bearing silicate phases (olivine, pyroxene or amphiboles) and Ca–phosphate phases (apatite), especially under slightly acidic conditions. Analysis of reacted phases by SEM shows little evidence of alteration of glassy material, whereas surfaces of Ca–Mg inosilicates, olivine and apatite show etched features indicative of dissolution. Results of the dissolution experiments suggest that, although these phases are relatively minor components of the ash, they contribute disproportionately to the overall weathering flux, and their reactivity may be particularly important in areas where physical weathering and erosion are constantly exposing new fresh surfaces available for chemical reaction.     

Iron isotope fractionation in oxic soils by mineral weathering and podzolization

Stable iron isotope ratios in three soils (two Podzols and one Cambisol) were measured by MC-ICPMS to investigate iron isotope fractionation during pedogenic iron transformation and translocation processes under oxic conditions. Podzolization is a soil forming process in which iron oxides are dissolved and iron is translocated and enriched in the subsoil under the influence of organic ligands. The Cambisol was studied for comparison, representing a soil formed by chemical weathering without significant translocation of iron. A three-step sequential extraction procedure was used to separate operationally-defined iron mineral pools (i.e., poorly-crystalline iron oxides, crystalline iron oxides, silicate-bound iron) from the soil samples. Iron isotope ratios of total soil digests were compared with those of the separated iron mineral pools. Mass balance calculations demonstrated excellent agreement between results of sequential extractions and total soil digestions. Systematic variations in the iron isotope signature were found in the Podzol profiles. An enrichment of light iron isotopes of about 0.6‰ in δ⁵⁷Fe was found in total soil digests of the illuvial Bh horizons which can be explained by preferential translocation of light iron isotopes. The separated iron mineral pools revealed a wide range of δ⁵⁷Fe values spanning more than 3‰ in the Podzol profiles. Strong enrichments of heavy iron isotopes in silicate-bound iron constituting the residue of weathering processes, indicated the preferential transformation of light iron isotopes during weathering. Iron isotope fractionation during podzolization is probably linked to the ligand-controlled iron translocation processes. Comparison of iron isotope data from eluvial and illuvial horizons of the Podzol profiles revealed that some iron must have been leached out of the profile. However, uncertainties in the initial iron content and iron isotopic composition of the parent materials prevented thorough mass balance calculations of iron fluxes within the profiles. In contrast to the Podzol profiles, the Cambisol profile displayed uniform δ⁵⁷Fe values across soil depth and showed only a small enrichment of light iron isotopes of about 0.4‰ in the poorly-crystalline iron oxide pool extracted by 0.5 M HCl. This work demonstrates that significant iron isotope fractionations can occur during pedogenesis in oxic environments under the influence of organic ligands. Our findings provide new insights into fractionation mechanisms of iron isotopes and will help in the development of stable iron isotopes as tracers for biogeochemical iron cycling in nature.     

化学作用是干旱地区岩石风化的主要因素——蒸发和淋漓模拟实验

在相同的物理化学(常温、常压、氧化)环境中,用大气降水分别对两块相似的硫化物矿石样品进行蒸发或淋漓实验,模拟干旱地区和潮湿地区的岩矿石风化作用。实验共进行603d。实验结果显示:经蒸发实验的样品无论是硬度、颜色和矿物组成等都发生了明显的变化,而经淋漓实验的样品无论硬度、颜色和矿物成分等基本保持实验前的特征;作蒸发实验浸泡液的pH值先降后升,最后稳定在6.5～7,而作淋漓实验淋漓液的pH先降,然后稳定于5左右,浸泡液的阳离子浓度却比淋漓液的高。实验结果表明蒸发作用比淋漓作用更容易使岩矿石风化。蒸发作用主要是化学反应。所以,这一实验结果向干旱地区主要是物理风化的传统认识提出了的挑战。     

Silicate and carbonate mineral weathering in soil profiles developed on Pleistocene glacial drift (Michigan, USA): Mass balances based on soil water geochemistry

Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition.Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO₂. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg²⁺/Ca²⁺ ratio of 0.4.Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca²⁺ and Mg²⁺ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg²⁺ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.     

Acidification processes and soil leaching influenced by agricultural practices revealed by strontium isotopic ratios

In natural river systems, the chemical and isotopic composition of stream- and ground waters are mainly controlled by the geology and water-rock interactions. The leaching of major cations from soils has been recognized as a possible consequence of acidic deposition from atmosphere for over 30 years. Moreover, in agricultural areas, the application of physiological acid fertilizers and nitrogen fertilizers in the ammonia form may enhance the cation leaching through the soil profile into ground- and surface waters. This origin of leached cations has been studied on two small and adjacent agricultural catchments in Brittany, western France. The study catchments are drained by two first-order streams, and mainly covered with cambisoils, issued from the alteration and weathering of a granodiorite basement. Precipitations, soil water- and NH₄ acetate-leachates, separated minerals, and stream waters have been investigated. Chemical element ratios, such as Ba/Sr, Na/Sr and Ca/Sr ratios, as well as Sr isotopic ratios are used to constrain the relative contribution from potential sources of stream water elements.Based on Sr isotopic ratio and element concentration, soil water- and NH₄ acetate leaching indicates (1) a dominant manure/slurry contribution in the top soil, representing a cation concentrated pool, with low ⁸⁷Sr/⁸⁶Sr ratios; (2) in subsoils, mineral dissolution is enhanced by fertilizer application, becoming the unique source of cations in the saprolite. The relatively high weathering rates encountered implies significant sources of cations which are not accessory minerals, but rather plagioclase and biotite dissolution.Stream water has a very different isotopic and chemical composition compared to soil water leaching suggesting that stream water chemistry is dominated by elements issued from mineral and rock weathering. Agriculture, by applications of chemical and organic fertilizers, can influence the export of major base cations, such as Na⁺. Plagioclase dissolution, rather than anthropogenically controlled soil water, seems to be the dominant source of Na⁺ in streams. However, Ca²⁺ in streams is mostly derived from slurries and manures deposited on top soils, and transferred into the soil ion-exchange pool and stream waters. Less than 10% of Na⁺, 5-40% of Sr²⁺ and 20-100% of Ca²⁺ found in streams can be directly derived from the application of organic fertilizers.     

Influence of landscape position and vegetation on long-term weathering rates at the Hubbard Brook Experimental Forest, New Hampshire, USA

The spatial variability of long-term chemical weathering in a small watershed was examined to determine the effect of landscape position and vegetation. We sampled soils from forty-five soil pits within an 11.8-hectare watershed at the Hubbard Brook Experimental Forest, New Hampshire. The soil parent material is a relatively homogeneous glacial till deposited ∼14,000 years ago and is derived predominantly from granodiorite and pelitic schist. Conifers are abundant in the upper third of the watershed while the remaining portion is dominated by hardwoods. The average long-term chemical weathering rate in the watershed, calculated by the loss of base cations integrated over the soil profile, is 35 meq m⁻² yr⁻¹—similar to rates in other ∼10 to 15 ka old soils developed on granitic till in temperate climates. The present-day loss of base cations from the watershed, calculated by watershed mass balance, exceeds the long-term weathering rate, suggesting that the pool of exchangeable base cations in the soil is being diminished. Despite the homogeneity of the soil parent material in the watershed, long-term weathering rates decrease by a factor of two over a 260 m decrease in elevation. Estimated weathering rates of plagioclase, potassium feldspar and apatite are greater in the upper part of the watershed where conifers are abundant and glacial till is thin. The intra-watershed variability across this small area demonstrates the need for extensive sampling to obtain accurate watershed-wide estimates of long-term weathering rates.     

A Review of the Methods and Controls of Soil Weathering Rates

The study of soil weathering processes College of Resources and Environment, rates and the associated influencing factors is crucial for understanding of the feedbacks between soil and environment, which will provide a basis for predicting soil behavior and evolution trend in the ecosystem under natural and anthropogenic forcings. This is also important for the effective management of soil resources. This article reviewed the methods for measuring soil weathering rates (including simulating leaching experiment, model calculation, isotope technique, element depletion and geochemical mass balance) and the influencing factors (including climate, organism, parent material, relief, time and human activities). In view of the serious degradation of soil resources, we proposed the challenge and opportunity of the research of soil weathering. The future study should focus on the critical processes, rates and the associated environmental thresholds of soil weathering under varying natural conditions and intensive human perturbations, including the establishment of the quantitative relationship between the weathering rates calculated by different methods, the analysis and interpretation of synergistic effects among multiple influencing factors, and the modeling and prediction of changing tendency of weathering rates under the impacts of both climatic changes and human activities, in order to guide the sustainable management of soil resource and mitigation of global change.     

Time evolution of the mineralogical composition of Mississippi Valley loess over the last 10 kyr: Climate and geochemical modeling

Anthropogenic and natural climate change affect processes in the atmosphere, biosphere, hydrosphere, and pedosphere. The impact of climate on soil evolution has not been well-explored, largely due to slow rates and the complexity of coupled processes that must be observed and simulated. The rates of mineral weathering in loess deposited 23 kyr ago and experiencing soil formation for 13 kyr are explored here using the WITCH model for weathering and the GENESIS model for climate simulation. The WITCH model, which uses rigorous kinetic parameters and laws with provision for the effect on rates of deviation from equilibrium, can successfully simulate the depletion profiles in the soil for dolomite and albite if soil CO₂ is assumed to rise over the last 10 kyr up to about 30-40× the present atmospheric pressure, and if the solubility product of the Ca-smectite is assumed equal to that of an Fe(III)-rich Ca-montmorillonite. Such simulations document that dissolution behavior for silicates and carbonates are strongly coupled through pH, and for Ca-smectite and feldspars through dissolved silica. Such coupling is not incorporated in simple geometric and analytical models describing mineral dissolution, and therefore probably contributes to the long-standing observation of discrepancies among laboratory and field mineral dissolution rates.     

The influence of soil age on calculated mineral weathering rates

Mineral weathering rates for two chronosequences of soils have been calculated using an empirical method based on mineralogy, the depletion of elements relative to a conservative element and the computer model PROFILE. Weathering rates calculated by the empirical and depletion methods showed a decrease in rates with soil age whilst those calculated using the PROFILE model showed an increase with soil age. The counter intuitive PROFILE prediction is due to the use of surface area—normalised reaction rate coefficients which assume that: 1) mineral reactivity is constant with time and, 2) total mineral surface area is equivalent to reactive surface area.In Europe, mineral weathering rates in soils are an important input in determining levels of acid deposition above which ecosystem damage will occur (critical loads). As soils in Great Britain and much of NW Europe can range in age from <10³ to >10⁵ a, it is suggested that, until computer models can take account of soil age and the concomitant changes in mineral reactivity and surface area, modelled weathering rates will be subject to large uncertainties     

Estimation of weathering rates for critical load calculations in Finland

 The formation of base cations through mineral weathering in forest soils is one of the key parameters in calculating critical loads. Weathering rates in Finland have been estimated using a variety of methods. In the first approach, three weathering rate categories were assigned to soils according to the bedrock type. The second approach was based on an empirical relationship obtained from Swedish field studies. Changes in zirconium content through the soil profile were used to estimate element losses in soil after deglaciation. These calculated losses correlated well with the total calcium and magnesium concentrations in till C-horizons and the effective temperature sum (ETS). Comprehensive geochemical data for the parent till fine fraction (<0.06 mm) was available through the reconnaissance scale till geochemical mapping program of the Geological Survey of Finland (GSF). The equations obtained from Swedish studies were based on the use of the coarse (<2.0 mm) till fraction, and the differences in element concentrations between the fine and coarse size fractions remained a potential source of uncertainty estimating overall weathering rates. In the third approach, new geochemical data from the <2.0 mm till fraction from southern Finland were used to make new weathering rate estimates. The use of soil geochemistry instead of bedrock map classification clearly led to an improvement in the estimates of soil weathering rates in glacied terrains. The use of the fine till fraction (<0.06 mm) in the zirconium approach generally resulted in overestimations of the weathering rate. The new geochemical data for the coarse till fraction (<2 mm) are now consistent with the input requirements of the zirconium method, although the results still require further evaluation. Finnish soil profiles have a shorter weathering history than most of the Swedish ones and the uppermost layer in Finnish podsols has in some cases developed in a different till layer than the C-horizon. Received: 15 October 1995 · Accepted: 8 March 1996     

海南岛不同地质背景下的土壤类型、质量特征和作物适宜性

文章利用海南岛SOTER数据库及自动土地评价模型ALES评价结果,对海南岛4种主要母岩上发育的土壤类型、土壤性质及香蕉种植适宜性与母质的关系进行了分析。海南岛不同母岩上土壤类型的发育呈现多样性,土壤类型的分布明显受到母岩类型、成土年龄、成土环境等因素的影响。酸性火成岩上主要发育有雏形土和富铁土,基性岩上则主要是发育良好的铁铝土,碎屑岩上主要是雏形土,而海相沉积物由于土壤形成时间的差异出现了多样的土壤类型。在海南岛湿热的气候条件下,原生母岩上发育的土壤,尽管成土母岩成分各不相同,但一些土壤性质已经没有明显差别,如交换性钙、镁、钠等,部分土壤化学性质如交换性钾的含量继承了母岩特性。各种母岩上发育的土壤,在自然条件下,适宜香蕉种植的比例都很低,但基性火成岩和海积物上发育的土壤,更容易受到人为管理措施的影响,如果满足一定的技术和经济投入,海南岛热带作物的种植潜力可以得到进一步的挖掘。     

地壳风化速率研究综述

地壳风化速率研究的理论基础是质量守恒原理和溶液与矿物反应动力学法则。元素在风化过程中的行为受多种因素控制，主要包括基岩风化量、大气沉降量、径流量、生物的输出数量和人为输入量（如施肥）。硅酸盐矿物化学风化过程中，矿物与溶液之间总的化学反应速率是单个反应速率之和，其中涉及到 3个关键参数，即：酸中和能力（ANC）、基本阳离子/无机铝（BC/Al无机）比值和临界负荷（CL）。风化速率的研究主要采用四种方法，即PROFILE模型、基本阳离子损耗、元素输入-输出指数和Sr同位素比值等。PROFILE模型是一个稳定态的综合土壤化学模型，矿物的分解速率、矿物的暴露表面积、土壤水饱和度和土壤层厚度决定着该矿物的风化速率，总的风化速率为各种矿物的风化速率之和。元素损耗，主要是基本阳离子（Ca、Na、K和Mg）的损耗，假设Ti、 Zr和Nb在成土过程中含量稳定并不参与风化反应，那么对于给定的土壤层，化学风化损耗的基本阳离子可以通过比较土层与成土母质之间元素组成的差异来计算。输入-输出指数的假设前提是研究的流域处于稳定状态，一般认为输入指数是大气沉降，输出指数是河流搬运溶解部分、悬浮的非岩屑成因部分和生物营养净吸收部分。Sr同位素在生物和化学作用过程中并不分馏，不同生态系统阳离子场中Sr同位素组成是大气和矿物风化来源的Sr的混合物。     

Chemical Weathering Rates, Erosion Rates and Mobility of Major and Trace Elements in a Boreal Granitic Till

Chemical weathering rates and erosionrates of granitic till in northern Sweden have beenestimated. The present-day chemical weathering rate iscompared with the long-term average weathering ratesince the last deglaciation approximately 8,700 yearsago. Also, the present-day release rates of major andtrace elements due to chemical weathering are comparedwith the mobility of these elements in a spodosolprofile as shown by soil water samples from the vadozezone. The estimation of the past weathering rate isbased on elemental depletion trends in a soil profile(typic haplocryod), whereas the present weatheringrate is based on elemental input/output budgets in asmall catchment (9.4 km²). The long-term averagechemical erosion rate, expressed as the sum of majorelement oxides (SiO₂, Al₂O₃, CaO,Fe₂O₃, K₂O, MgO, MnO, Na₂O,P₂O₅, TiO₂), was estimated to be4.9 gm^-2 yr^-1. The long-term base cation(Ca²⁺, Mg²⁺, Na⁺, K⁺) depletionwas 0.325 keq ha^-1 yr^-1. The currentchemical erosion rate was estimated to be2.43.0 g ^-2 yr^-1, which is at least an order ofmagnitude higher than the rate of physical erosion,and the base cation flux due to chemical weathering is0.356–0.553~keq ha^-1 yr^-1. However,0.074 keq ha^-1 yr^-1 of this flux may be related tocation exchange processes induced by atmospheric inputof acid rain. There is no evidence for any recentlyincreased weathering rate of silicates in this area.The inputs of Cd, Cu, Ni and Zn exceed the outputs,and hence, these elements are currently accumulatingin the soil.There is a distinct seasonal variation in thechemical composition of the soil water. Results fromthe soil water samples show that Na, followed by Siand S (Cl was not measured), are the most mobileelements in the spodosol profile between the E-horizonand the C-horizon, and that Al and Fe were the leastmobile elements. However, there is no simplerelationship between the mobility of an element in thespodosol profile and the current release rate due toweathering of that element. This fact may haveimplications for the validity of the comparisonbetween the past and present weathering rates asperformed in this study.     

Geochemical and mineralogical investigations of the Lower Jurassic flint-clay bearing Mishhor and Ardon Formations,Makhtesh Ramon,Israel

The Lower Jurassic section at Makhtesh Ramon, in the northeastern Negev of Israel, comprises a sequence of fluviatile sediments of laterite composition. Post-depositional chemical weathering has resulted in marked facies changes whereby the clastic sequence passes laterally into high-alumina flint clays and bauxites (Goldbery, 1979). A geochemical and mineralogical investigation was initiated on 216 samples from several key sections of the facies change to obtain a more refined definition of the diagenetic overprint, to reconstruct the history of chemical weathering and finally to recognize the parent material of the unaltered laterite sediments.Results are presented herein on major and trace-element composition, normative mineralogical composition, kaolinite crystallinity and porosity and density measurements. Kaolinite crystallinity values proved to be a good indicator of intensity of leaching, showing a marked decline in ordering with increase of diagenetic reorganization. On the basis of mineralogical parameters it was possible to subdivide the section of flint clays and bauxites, generated under karstic conditions, into four units. Bivariate plots of Al₂O₃ vs. several elements within the section, plotted into four distinctive fields coinciding with the subdivision. Enrichment/depletion ratios, calculated from the element concentrations within these flint clays against element concentrations of the clastic parent material of the karstic infill, led to the reconstruction of a multi-cyclic leaching event, whose “signature” is left in each of the four units. At least 3 individual episodes of leaching, related to a rising water table and punctuated by “still-stands” could be recognized.Zr/TiO₂: Nb/Y plots of stable elements, using the diagram of Floyd and Winchester (1978) for determination of source rocks, indicated a rhyolite or alkaline rhyolite provenance for the clastic laterite detritus.     

方解石和钾长石在模拟蚯蚓肠液中的初始溶解动力学机理及意义

蚯蚓肠道内小分子有机酸与摄入的土壤矿物相互作用,加速矿物溶解。摄入的土壤在蚯蚓肠道内平均停留时间约为12 h,不足以使土壤矿物产生显著的溶解特征,因此这一过程难以在蚯蚓体内进行评估。本研究通过体外实验控制pH值和有机酸浓度,模拟蚯蚓肠道中有机酸对土壤中常见矿物的溶解反应,探讨了方解石和钾长石在蚯蚓肠道环境中的初始溶解动力学。研究发现,矿物在混合有机酸中的溶解速率比在纯水中高一个数量级,说明有机配体和质子促进了矿物溶解。溶解速率及粒度分析表明,方解石(CaCO₃)溶解速率不受溶解过程中粒度变化的影响,而钾长石(KAlSi₃O₈)粒度在溶解期间未出现显著变化。在此基础上,采用初始速率法模拟了钾长石的初始溶解动力学,计算得出的溶解速率表明钾长石在溶解初期主要为表面K~+的释放。使用缩核模型(shrink core model)和Hixson-Crowell模型对方解石溶解过程进行动力学解析,发现方解石的溶解主要受溶液中反应物内扩散的速率影响。这定量描述了两种矿物在有机酸溶液和纯水中的溶解差异。现有研究表明,有机配体和质子协同促...