微生物及其碳酸酐酶对岩溶土壤系统钙镁元素淋失的影响

通过室内模拟土壤- 灰岩岩溶系统,对不同微生物处理条件下的土柱进行降水淋滤,系统监测了淋出液的pH、电导率、Ca2+ 、Mg2+ 以及碳酸酐酶( C A)活性。结果表明,微生物对该模拟系统Ca、Mg 元素迁移有较大促进作用。扫描电镜显示,埋入经微生物处理土柱的试片表面较对照(未埋入土柱和埋入灭菌土柱的试片)有明显侵蚀现象。另一方面,各处理的淋出液中均检测出不同程度的C A活性,说明土柱中的微生物产生了胞外CA并被淋出。相关分析表明淋出液中CA平均活性与Ca2+ 总淋失量之间存在较好的正相关关系,说明CA是影响Ca 元素淋失的主要因素。对其进行深入研究将有助于解释生物岩溶的机理。      

不同种类微生物及其碳酸酐酶对CO_2-H_2O-碳酸盐系统中碳酸盐岩的溶蚀作用

以从西南岩溶地区土壤中筛选出来的产碳酸酐酶(CA)的典型细菌、真菌和放线菌为材料,研究比较了不同种类微生物及其CA对CO2-H2O-碳酸盐系统中碳酸盐岩的溶蚀作用。结果表明,实验所用的3种典型微生物均对石灰岩和白云岩有明显溶蚀作用,真菌的溶蚀效果最显著,而且微生物CA对石灰岩具有明显的酶促溶蚀效果。微生物对石灰岩的溶蚀能力强于白云岩,加入石灰岩的真菌试验组中Ca2+浓度比加入白云岩的真菌试验组高8.0%,而且,真菌CA对白云岩的溶蚀能力明显强于石灰岩。上述结果为研究微生物及其CA在岩溶碳汇中的作用提供了科学依据。     

微生物碳酸酐酶对石灰岩的溶蚀驱动作用研究

来源于西南几个不同类型岩溶地区土壤样品分离出来的微生物菌株中,有很多能够产生分泌胞外碳酸酐酶。以一株编号为GLCa102的菌株为代表,模拟岩溶自然环境条件,研究其胞外碳酸酐酶对灰岩的溶蚀驱动作用。结果表明微生物碳酸酐酶能使灰岩溶出的导电离子总量和[Ca2+ ]提高40%以上,从而对灰岩有显著的酶促溶蚀驱动作用。本研究表明微生物碳酸酐酶在生物岩溶中有重要的作用和地位,同时为深入研究生物对石灰岩的溶蚀作用提供了一定的科学依据。      

土壤入渗对阜新市北部浅层地下水总硬度影响的淋滤实验

本次室内土柱淋滤实验通过改变Na~+、H~+、NH_4~+浓度来模拟现实生活中不同浓度的生活污水、酸雨及农业施肥灌溉对浅层地下水总硬度的影响过程。实验结果表明淋滤液浓度越高,所对应的淋出液的总硬度峰值就越高。相同浓度的Na~+、H~+、NH_4~+进行土柱淋滤实验时,NH_4~+所对应的淋出液总硬度的峰值最大,H~+次之,Na~+最小且NH_4~+所对应的整个实验用时最短,在相同浓度单一离子作用下NH_4~+对浅层地下水硬度的影响更加明显。     

碳酸盐岩红土风化剖面的淋滤试验研究—— 以贵州遵义和平坝剖面为例

采用人工配制的饱和碳酸水溶液对贵州省安顺、遵义两个典型红土风化剖面的样品柱,在常温、常压下进行长约100小时的淋滤试验。对溶液中10种元素进行检测表明:石灰岩及其溶滤层比白云岩及其溶滤层Ca、Mg的溶出量大2～5倍;成土物质Al、Si、Fe、Mn等元素有微量的溶出,且红土化程度较低的石灰岩风化剖面较红土化程度较高的白云岩剖面的溶出量大几倍,遵义剖面在碳酸水的淋滤下发生较明显的脱Si作用。试验前后淋滤液的酸度值发生显著变化,pH值由4.12～4.17变为6.86～8.09。      

添加有机物料对岩溶系统中碳转移及灰岩溶蚀的影响研究

以贵州茂兰一种灌丛土壤和一种农业用地土壤为研究对象,设置了添加和不添加有机物料处理,进行了岩溶作用与土壤碳转移的模拟试验。结果表明,土壤CO2 呼吸排放、土壤淋滤液HCO-3 排泄及灰岩溶蚀均响应于有机物料的添加。对于无机离子Ca2+ 、Mg2+来说,在不添加有机物料情况下,其淋出过程表现为一个较高的活跃可迁移库的释放过程及随后较低风化淋滤的稳定释放过程。在添加有机物料条件下,分解释放的Ca及CO2产生的HCO-3的排释滞后于土壤呼吸15天以上。添加有机物料下,灰岩溶蚀量均有一定幅度的提高,但Ca( Mg )及HCO-3的排释大大增强,这一方面表明生物可利用性的碳源的加入促进了系统中岩溶作用,并强烈驱动土壤中可交换Ca、Mg的排释;另一方面,由于土壤中因呼吸增强而形成的高CO2在湿润条件下溶解成为HCO-3 - C排泄,而大大促进土壤碳转移的汇效应。本文的研究结果说明,自然土壤因植被的破坏或林地转变为农地,可能使岩溶系统的汇效应减弱。      

酸雨淋溶下MICP固化铅污染土的淋滤特性研究

酸雨可与MICP矿化作用过程中生成的碳酸盐反应,破坏材料的结构强度,使被固定的重金属离子再次释放,但该技术在酸雨环境下的研究较少,耐酸腐蚀性尚不明确,因此对酸雨入渗作用下MICP固化重金属污染土的淋滤特性的研究具有现实意义。本文设计了pH值为3.5、4.5、5.6的3种典型的酸雨条件,用pH值为7.5的去离子水作对照,通过土柱淋滤的方法对MICP固化粉土进行了实验研究,分析不同酸雨pH值对MICP固化铅污染土样的强度、pH值、Pb²⁺、Ca²⁺淋出量及Pb²⁺赋存形态的影响。结果表明：随酸液pH值降低,MICP固化试样的强度降低,淋出液pH值降低,Pb²⁺、Ca²⁺淋出量增加,固化试样中可交换态的Pb²⁺增加,当pH值为5.6时,试样受酸雨影响较小,pH值降为3.5时,试样变化显著。     

硅藻碳酸酐酶对石灰岩岩溶的作用及其生态意义

碳酸酐酶(carbonic anhydrase,CA)是一种广泛存在的金属酶,催化CO2的水合反应。硅藻分泌的碳酸酐酶能促进石灰岩的溶蚀。对硅藻碳酸酐酶在石灰岩岩溶中的作用进行了探讨。结果表明,硅藻碳酸酐酶在生物岩溶中具有重要的作用和地位,同时为深入研究生物对石灰岩的溶蚀作用提供了一定的科学依据。     

碳酸酐酶胞外酶影响下的岩溶湖泊微藻碳汇研究

以岩溶湖泊——红枫湖的微藻为研究对象,通过添加两种标记稳定碳同位素组成的无机碳进行室内模拟岩溶环境条件;并通过添加不同浓度的乙酰唑胺（AZ）,来模拟岩溶湖泊中碳酸酐酶胞外酶活性差异的各类微藻。重点监测微藻蛋白质含量及其稳定碳同位素组成变化等指标,计算其对不同来源无机碳的吸收利用份额,并结合微藻的生物量生长指标,最终计算出碳酸酐酶胞外酶活性差异的各种微藻的碳汇能力。结果显示:在岩溶湖泊的自然水体中,碳酸酐酶胞外酶活性强的微藻碳汇能力是缺乏碳酸酐酶胞外酶的微藻碳汇能力的5倍。碳酸酐酶胞外酶对微藻光合碳汇能力的影响显著。      

CO2浓度梯度对两种岩溶微藻碳酸酐酶活性的影响

以经岩溶水驯化的小球藻（Chlorella vulgaris）和喜钙念珠藻(Nostoc calcicola Breb.)为实验对象,在封闭体系中用Willbur和 Anderson 方法比较研究两种不同微藻在不同CO2浓度下碳酸酐酶活性变化情况。结果表明:在低于3%CO2浓度的环境中岩溶微藻可通过快速调节自身碳酸酐酶活性来应对CO2升高带来的生境影响,在影响最大的2.5%的环境下小球藻与喜钙念珠藻碳酸酐酶活性分别提高了1.46倍和2.12倍;岩溶微藻应对CO2浓度增大带来的pH下降有着重要的恢复作用,随培养时间增长培养环境中的pH得到恢复;随着CO2浓度的增大,岩溶因子对碳酸酐酶有着重要的影响;培养48 h时Ca2+与喜钙念珠藻碳酸酐酶的相关性最高,而电导率（EC）与小球藻碳酸酐酶相关程度最高。      

中国东部玄武岩风化土壤的粘土矿物及碳 汇地球化学研究

     玄武岩风化是大气CO2 的一个主要碳汇过程,气候条件是影响玄武岩风化和固碳速率的重要因素。该文选择中国东 部不同气候带的新生代玄武岩典型风化剖面,进行了粘土矿物和常量元素分析。结果显示,在内蒙古-海南岛的采样区间内, 随着气候条件由干冷向暖湿转化,风化剖面中粘土矿物组合呈现蒙脱石+ 伊利石+ 高岭石→蒙脱石+ 高岭石→高岭石+ 三水 铝石的转变。剖面中土壤元素得失状况也显示出相应的规律,由于存在粉尘输入与风化淋滤作用的综合影响,在干冷的内 蒙古地区,粉尘对于Ca,K,Na,Si 等元素的输入量大于这些元素的淋失量;在山东地区,Ca,K,Na 元素开始快速淋失, 大于粉尘的输入量;在苏皖地区,Si 元素的淋失量开始小于粉尘输入量;而在湿热的海南地区,风化作用强烈,Si显示出 大量淋失的特点,碱性元素几乎全部流失。根据元素的相对得失率和北方粉尘平均组分的校正,初步估算了研究区内玄武 岩风化对大气CO2 的消耗速率,其数值在5.37~181.00 t（km2·a）之间,与Dessert 等（2003）的研究结果大致相当。     

Evaluation of phosphorus leaching from contaminated calcareous soils due to the application of sheep manure and ethylenediamine tetraacetic acid

Organic amendment application to heavy metal contaminated soils may contribute to leaching of phosphorus (P). The objectives of this study were to determine the influence of sheep manure and ethylenediamine tetraacetic acid (EDTA) on the P leaching from a wide range of calcareous contaminated soils. Glass tubes, 4.9 cm diameter, and 40 cm long, were packed with contaminated soil. The resulting 20 cm long column of soils had bulk density of 1.3–1.4 g cm⁻³. The columns were leached with distilled water, 0.01 M EDTA, 0.01 M CaCl₂ or sheep manure extract (SME) solutions. The breakthrough curves for P were different and the amounts of P leached varied considerably between different soils and leaching solutions. The amounts leached with SME were less than the amount added through the SME, indicating that some P was retained by the soil, mainly due to preliminary sorption of organic ligands on to the soil with the creation of new sorbing surfaces. The amount leached with EDTA solution varied from 9.9 to 46.3% of the extractable P when 15 pore volumes had passed through the column. Low amounts of P were leached by 0.01 M CaCl₂, which is likely to be due to the high concentration of soluble Ca used in the solution. Thus, among leaching solutions the application of EDTA and SME on contaminated calcareous soils might enhance the mobility of P and large amounts of P will be leached, leading to contamination of ground and surface waters.     

The role of microalgae and their carbonic anhydrase on the biological dissolution of limestone

This study aims to investigate the effect of microalgae and their carbonic anhydrase (CAex) on limestone dissolution. The dynamics of Ca²⁺ and Mg²⁺ release, the model for the amount of Mg²⁺ released and biological cumulative effect time by the microalgae Chlamydomonas reinhardtii (CR) and Chlorella pyrenoedosa (CP), and the algal stable carbon isotopic composition (δ¹³C) in the presence and absence of the membrane-impermeable CAex inhibitor acetazolamide (AZ) were compared in a medium containing limestone. The amount of Mg²⁺ released from the limestone in the treatment without AZ was more than that with AZ during the logarithmic phase. The amounts of Mg²⁺ release unit algal biomass and unit time in CR and CP were 3.37 × 10^?4 and 2.44 × 10^?4 mg/μg days in the treatment without AZ, respectively, and only 1.99 × 10^?4 and 2.19 × 10^?4 mg/μg days in the treatment with AZ, respectively. The biological dissolution of the algae increased with increasing algal CAex activity. The variation of Ca²⁺ was influenced by reprecipitation, and the algal limestone dissolution cannot be shown distinctly. The CAex of the microalgae may be beneficial for CaCO₃ reprecipitation, and the δ¹³C values of the algal cells with AZ were lower than those without AZ. Therefore, AZ not only can inhibit limestone dissolution by inhibiting microalgal growth, but also can reduce limestone dissolution by decreasing CAex catalysis. The results suggest the important influence of microalgae and their CAex on the biokarst process.     

Potassium leaching in undisturbed soil cores following surface applications of gypsum

Displacement studies on leaching of potassium (K⁺) were conducted under unsaturated steady state flow conditions in nine undisturbed soil columns (15.5 cm in diameter and 25 cm long). Pulses of K⁺ applied to columns of undisturbed soil were leached with distilled water or calcium chloride (CaCl₂) at a rate of 18 mm h⁻¹. The movement of K⁺ in gypsum treated soil leached with distilled water was at a similar rate to that of the untreated soil leached with 15 mM CaCl₂. The Ca²⁺ concentrations in the leachates were about 15 mM, the expected values for the dissolution of the gypsum. When applied K⁺ was displaced with the distilled water, K⁺ was retained in the top 10–12.5 cm depth of soil. In the undisturbed soil cores there is possibility of preferential flow and lack of K⁺ sorption. The application of gypsum and CaCl₂ in the reclamation of sodic soils would be expected to leach K⁺ from soils. It can also be concluded that the use of sources of water for irrigation which have a high Ca²⁺ concentration can also lead to leaching of K⁺ from soil. Average effluent concentration of K⁺ during leaching period was 30.2 and 28.6 mg l⁻¹ for the gypsum and CaCl₂ treated soils, respectively. These concentrations are greater than the recommended guideline of the World Health Organisation (12 mg K⁺ l⁻¹).     

菜田施肥(化肥)对地下水氮污染影响的实验研究

为研究菜田施肥（化肥）对地下水氮污染的影响,进行了２个土柱模拟菜田施肥（化肥）残存量的实验．结果表明,土柱中化肥残存量的７２．０８％和４７．４４％从渗出水中流出．依据实验数据将实验过程分为３个可能阶段：第１阶段,化肥中的ＮＨ＋４被土壤吸附,并交换出土壤中的Ｋ＋＋Ｎａ＋,Ｃａ２＋和Ｍｇ２＋,使之进入渗出水中;第２阶段,为硝化作用增强的阶段,表现为土柱渗出水中ＮＯ－３的质量浓度比注入水有大幅度增加;第３阶段,为硝化作用强度减弱的阶段,表现为渗出水中ＮＯ－３的质量浓度比注入水增加的幅度减小．     

Effect of NO2 in exhaust gas from an oxyfuel combustion system on the cap rock of a proposed CO2 injection site

A laboratory geochemical study was conducted using a drill core sample of cap rock from the Surat Basin, Australia, to investigate the effect of NO₂ contained in the CO₂ gas exhausted from the oxyfuel combustion process (oxyfuel combustion CO₂) on the cap rock. A gas (CO₂ containing NO₂) was prepared to simulate the exhaust gas produced from the oxyfuel combustion process. Two types of gases (pure CO₂ and CO₂ containing SO₂) were also prepared as reference gases. The effect of NO₂ on cap rock was studied experimentally using these gases. No differences in the amounts of leached ions and pH changes for CO₂ containing NO₂ (36 ppmv), pure CO₂, and CO₂ containing SO₂ (35 ppmv) existed. The pH values decreased immediately after CO₂ gas injection but increased with time as a result of mineral buffering. Leaching of Fe, Mg, Ca, and K was suggested to have occurred as the result of dissolution of Fe-chlorite, prehnite and illite-smectite mixed layer clay in the shale sample. The amounts of Ca, Fe, and Mg leached with CO₂ containing NO₂ (318 ppmv) were higher than those for pure CO₂. For the mixture containing 318 ppmv NO₂, the pH increased more than that for the other gas conditions immediately after the pH fall at the start of the experiment, because oxidation-reduction reactions occurred between Fe²⁺ and NO₃⁻. Moreover, the results indicated that some of the leached Ca and Fe were deposited on the shale sample because of the pH increase. Therefore, we concluded that the effects of NO₂ on mineral dissolution and pH changes of formation water are negligible when oxyfuel combustion CO₂ containing about 30 ppmv of NO₂ is injected into an underground aquifer. In addition, even if about 300 ppmv NO₂ is accidentally injected into the underground aquifer, mineral dissolution is suppressed due to the buffering of pH decrease after gas injection.     

泥沙颗粒表面电荷特性及其对干容重影响试验研究

采用黄河及长江中的沙样在不同Ca2+浓度下分别进行电位滴定试验和干容重试验,得到以下结论:①随Ca2+浓度的增加,泥沙颗粒表面负电荷先不断减少然后趋于不变。②Ca2+对泥沙淤积干容重的影响可分为三个阶段:第一阶段干容重减小;第二阶段增加并达到最大值;第三阶段减小最后趋于不变。③在Ca2+浓度相同条件下,泥沙浓度对淤积干容重的影响根据所加Ca2+浓度不同也呈现不同的变化。④Ca2+浓度、泥沙浓度相同时,中值粒径越大干容重越大,且中值粒径大的泥沙干容重达到最大值所需Ca2+少。⑤在不同Ca2+浓度下泥沙颗粒由于表面电荷不同造成静电斥力不同,同时表面水膜作用力也不同,二者共同作用使得干容重体现不同的变化。     

Effect of sheep manure and EDTA on the leaching of potassium from heavy metals contaminated calcareous soils

In this study, we examined the movement of potassium (K) in columns of contaminated calcareous soils by sheep manure and ethylene diamine tetraacetic acid (EDTA). Glass tubes, 4.9 cm in diameter and 40 cm in length, were packed with contaminated soils. The resulting 20-cm long column of soil had a bulk density of 1.3–1.4 g cm⁻³. Columns were leached with distilled water, 0.01 M EDTA, 0.01 M CaCl₂, and sheep manure extract solutions. The amounts of K leached varied considerably between different soils (sandy loam and loamy sand) and leaching solutions. The amount leached with EDTA solution, varied from 7.2 to 66.7% of the extractable K when 20 pore volumes had passed through the column. The breakthrough curves of K in the EDTA and CaCl₂ were approximately similar, indicating they have similar ability to displace K from these contaminated calcareous soils. Thus, among leaching solutions application of EDTA and CaCl₂ on contaminated soils might enhance the mobility of K and large amounts of K will be leached.     

Numerical modeling of the development of a preferentially leached layer on feldspar surfaces

Compositional depth profiles in the leached layer of feldspar surfaces are usually interpreted by using analytical solutions which introduce oversimplifying assumptions. Here we present a general multicomponent interdiffusion numerical model for simulating cation release from a preferentially leached layer on feldspar surfaces in acid solutions. The numerical model takes into account interdiffusion, dissolution of the solid phase (represented by a moving boundary problem), and adsorption in the leached layer. Effective diffusion coefficients of ions vary with concentration along the leached layer. Governing equations of ions diffusion in the leached layer are solved numerically with a finite element method implemented in a multicomponent reactive transport code, CORE^3D, previously verified against analytical solutions of compositional depth profiles. The numerical model is tested with published X-ray photoelectron spectroscopy (XPS) data on early development of compositional profiles of labradorite leached in pH 2 HCl solutions. Model parameters are estimated by fitting depth profiles of Ca and Al measured at 12, 26, 48, 72, and 143 h. The best fit is achieved with tracer diffusion coefficients of 4 × 10⁻¹⁸, 8 × 10⁻¹⁷, 3.4 × 10⁻¹⁷, and 7 × 10⁻¹⁸ cm²/s for H, Na, Ca, and Al, respectively, which fall within the range of values reported in the literature. Our estimate of the retreat velocity corresponding to the dissolution rate is 3 × 10⁻¹³ cm/s. Results of sensitivity runs show that computed compositional profiles are sensitive to most model parameters.