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。     

微藻无机碳利用在岩石风化及碳循环过程中的作用

岩溶碳汇呈现两种不同观点：（1）岩溶碳汇巨大,其机理在于岩溶区藻类及光合细菌利用碳酸氢根离子（${\rm{HCO}}_3^{-}$）实现光合作用,从动力学上加速了岩溶风化过程,促进大气CO2的溶解。（2）岩溶区碳酸盐岩的风化作用,产生${\rm{HCO}}_3^{-}$,随后产生等量的阳离子在海洋中进行碳酸盐岩的沉积作用,这仅仅体现的是碳酸盐岩的搬运作用,不能体现碳汇,在长期尺度上仅仅有硅酸盐岩风化产生净碳汇。文章抓住岩石风化产生${\rm{HCO}}_3^{-}$与微藻光合作用利用${\rm{HCO}}_3^{-}$的耦合点,分析了典型代表性水生生物——微藻在无机碳利用上对岩石风化及碳汇的影响。从微藻光合无机碳利用机制以及光合作用关键性酶－碳酸酐酶（CA）作用两方面,论证了微藻生长对岩石风化及其碳汇的的促进作用;同时论述高pH、高${\rm{HCO}}_3^{-}$的风化环境对微藻生长影响。获得以下新认识：（1）微藻通过胞外碳酸酐酶（CAex） 利用了大量${\rm{HCO}}_3^{-}$,加速岩石风化,并促使风化朝着形成${\rm{HCO}}_3^{-}$的方向进行;（2）微藻加速钙镁硅酸盐岩风化,风化溶出的Ca2+、Mg2+会促使碳酸盐岩的沉积,因此微藻加速硅酸盐岩风化形成净碳汇;（3）长时间尺度下,单纯的碳酸盐岩化学风化并不能直接产生净碳汇,但微藻对${\rm{HCO}}_3^{-}$利用使得碳酸盐岩风化朝着${\rm{HCO}}_3^{-}$转化方向进行,微藻参与碳酸钙沉积作用的同时转化无机碳为惰性有机碳,产生碳汇。故微藻通过CAex的作用,催化加速${\rm{HCO}}_3^{-}$与CO2之间的转化,形成水体${\rm{HCO}}_3^{-}$消耗的动力基础,微藻无机碳利用对岩石风化具有促进作用,从而调节大气CO2、浓度变化。基于当前研究,提出三点展望：（1）开展岩溶区区域水体系统的岩石风化、水生生物碳汇评估成为解决当前区域碳收支不平衡问题的关键;（2）查明岩石风化作用中生物作用碳转化机理及转化量,解决单纯的水化学径流法计算岩石风化碳汇精度不够问题;（3）构建光合生物参与下的新的评估方法,评估当前岩石风化在水生生物、水循环作用下的碳汇的时间尺度问题,厘清岩石风化碳汇在碳收支中的贡献。     

Comparative study of dissolution rate-determining mechanisms of limestone and dolomite

The dissolution rate-determining processes of carbonate rocks include: (1) heterogeneous reactions on rock surfaces; (2) mass transport of ions into solution from rock surfaces via diffusion; and (3) the conversion reaction of CO₂ into H⁺ and HCO ₃ ⁻ . Generally, it is the slowest of these three processes that limits the dissolution rate of carbonate rock. However, from experiment and theoretical analysis under similar conditions not only were the initial dissolution rates of dolomite lower by a factor of 3–60 than those of limestone, but also there are different dissolution rate-determining mechanisms between limestone and dolomite. For example, for limestone under the condition of CO₂ partial pressures dissolution rates increased significantly by a factor of about ten after addition of carbonic anhydrase (CA) into solution, which catalysed the conversation reaction of CO₂, whereas CA had little influence on dolomite dissolution. For dolomite, the increase of dissolution rate after addition of CA into solution appeared at Moreover, the enhancement factor of CA on dolomite dissolution rate was much lower (by a factor of about 3). In addition, when dissolution of both limestone and dolomite was determined by hydrodynamics (rotation speed or flow speed), especially under the dissolution of limestone was more sensitive to hydrodynamic change than that of dolomite. These findings are of significance in understanding the differences in karstification and relevant problems of resource and environment in dolomite and limestone areas.     

长江流域不同地质生态环境土壤碳酸酐酶活性、有机碳含量及其相关性

为了探讨流域岩溶生态系统土壤碳酸酐酶(CA)活性、有机碳含量及CA固碳之间的潜在关系,选取长江流域干流及支流沿岸不同地质生态环境下的10个样地,比较长江流域不同地质生态环境下表层土壤(0~20cm)中的碳酸酐酶(CA)活性与土壤有机碳(SOC)含量,并分析二者之间的关系。结果表明:(1)长江流域岩溶区的表层土壤CA活性要高于非岩溶区(P0.01),土壤CA活性的差异与样地的地质类型及植被类型不同有关;(2)位于岩溶区高场(GC)样地的年平均SOC含量最高(1.09%),而位于非岩溶区外洲(WZ)样地的年平均SOC含量最低(0.29%),而且总体比较而言,长江流域冬季表层土壤的平均SOC含量显著高于夏季(P0.01);(3)相关性分析结果显示,不同季节长江流域岩溶区表层土壤CA活性与SOC含量呈一定的正相关。研究结果为进一步研究流域岩溶生态系统土壤CA与土壤固碳能力之间的关系奠定了基础。     

振动荷载及温度对白云岩和石灰岩溶蚀影响试验研究

在岩溶地区,列车运行期间的振动会对白云岩和石灰岩的水岩作用过程产生影响,再加上复杂的外界条件,这一影响会更加显著。以桂北岩溶石山地区白云岩和石灰岩为研究对象,利用自主设计的试验装置进行室内模拟试验,分别研究振动荷载及不同温度条件对白云岩和石灰岩的溶蚀的影响规律。研究发现：①常温常压条件下,在静止的酸性溶液中,白云岩的溶蚀速率小于石灰岩;②在H⁺充足的条件下,随着温度（0~45 ℃）的升高,石灰岩和白云岩的溶蚀速率都会增大,温度变化对于白云岩溶蚀影响更为显著;③白云岩和石灰岩的溶蚀受振动条件的强烈影响,二者的溶蚀量都随着振动次数的增加而增大,且在相同振动条件下石灰岩的溶蚀速率始终大于白云岩。该研究可为桂北岩溶石山地区的工程设计和建设提供理论依据。     

碳酸酐酶及多肽类生物大分子与岩溶动力学理论的思考

岩溶动力系统是一个边界受制于已有地表地下岩溶形态,与地球四圈层有密切联系的开放系统.该系统在生物圈的主导作用下与水圈、大气圈及岩石圈(土圈)相互作用,产生物质循环和能量流动,发生水-岩-气作用,进而在全球碳循环中发挥积极作用.生命物质在水-岩-气过程中的作用机制,尤其碳酸酐酶快速催化水和二氧化碳反应过程,以及多肽类生物大分子提高方解石中镁含量能力的发现,使岩溶动力学理论得到进一步丰富和发展.因此,如何更好的将现代生命科学理论引入到岩溶动力学中,丰富和发展岩溶动力系统模型,并与生产实践相结合,是联合国教科文组织岩溶研究中心落户桂林之后岩溶动力学理论发展过程中面临的新课题.     

The role of background electrolytes on the kinetics and mechanism of calcite dissolution

The influence of background electrolytes on the mechanism and kinetics of calcite dissolution was investigated using in situ Atomic Force Microscopy (AFM). Experiments were carried out far from equilibrium by passing alkali halide salt (NaCl, NaF, NaI, KCl and LiCl) solutions over calcite cleavage surfaces. This AFM study shows that all the electrolytes tested enhance the calcite dissolution rate. The effect and its magnitude is determined by the nature and concentration of the electrolyte solution. Changes in morphology of dissolution etch pits and dissolution rates are interpreted in terms of modification in water structure dynamics (i.e. in the activation energy barrier of breaking water-water interactions), as well as solute and surface hydration induced by the presence of different ions in solution. At low ionic strength, stabilization of water hydration shells of calcium ions by non-paired electrolytes leads to a reduction in the calcite dissolution rate compared to pure water. At high ionic strength, salts with a common anion yield similar dissolution rates, increasing in the order Cl⁻ < I⁻ < F⁻ for salts with a common cation due to an increasing mobility of water around the calcium ion. Changes in etch pit morphology observed in the presence of F⁻ and Li⁺ are explained by stabilization of etch pit edges bonded by like-charged ions and ion incorporation, respectively. As previously reported and confirmed here for the case of F⁻, highly hydrated ions increased the etch pit nucleation density on calcite surfaces compared to pure water. This may be related to a reduction in the energy barrier for etch pit nucleation due to disruption of the surface hydration layer.     

Origin and geochemical evolution of groundwaters from Lastochka spa （Primorye, Russia）

Obtained new data on major element contents, trace and REE concentrations of sedimentary bedrock and groundwaters in Lastochka spa, along with isotope data, allow solving the problem of origin and evolution of these groundwaters. In the Lastochka area, located in Primorye region （Far East of Russia）, two types of groundwater are found： groundwater （TDS 0.2-0.4 g/L, pH 7.3-7.5） with lower pCO2 levels and groundwater with higher dissolved mineral content （TDS 3.7-4.7 g/L, pH 5.8-6.4） and high pCO2 levels. Our studies proved that both types of groundwaters originated from meteoric water and water-sedimentary stratum interaction has played a main role in forming chemical composition of waters. The main gas composition in the high pCO2 groundwater is CO2, which may as high as 98% of the total amount of all gas. The pressure of CO2, calculated using the water analysis data is at about 0.6 bar, while one measured in the field could reach 2.6 bar. The pressure of CO2 in groundwater with low TDS is 10.2 bar. Our δ^13C data [δ^13C （gas）=-6.22 versus PDB] indicate that most of the ^13C in the free CO2 of Lastochka spa is of upper mantle origin. Sedimentary bedrock is mainly sandstone with a good permeability. Dominate minerals are K-feldspar, quartz and plagioclase and secondary minerals are calcite, limonite, cericite and kaolinite. Our results indicate that the role of mantle CO2 gas is crucial for highly mineralized groundwater. This type of groundwater evolved only during water-rock-gas interaction. Extreme dissolution of albite in the presence of CO2 gas leads to the formation of lower pH and drastic accretion TDS and Na content in high pCO2 water. The violent difference in the trace element concentration in waters is caused by more intensive weathering of primary minerals in the presence of CO2 gas.     

不同土地利用类型下土壤碳酸酐酶剖面分异特征研究

利用pH计法来研究西南岩溶区4类土地利用类型11个样地20cm、40cm和60cm土层碳酸酐酶(Carbonic Anhydrase,CA)的剖面分异特征,并与非岩溶样地进行对比。结果表明:西南岩溶区不同土地利用类型不同土层的CA活性存在较大差异。在林地中,40cm和60cm土层的CA活性明显高于20cm土层;而在乔灌丛、灌丛和耕地中,土壤CA活性表现出60cm土层处最高,20cm土层处最低,并与弃耕地不同土壤层CA活性变化趋势截然相反,这是因为弃耕地受人类活动干扰导致土壤CA活性出现逆转。进一步分析还可以看出林地、乔灌丛、灌丛和耕地4种土地利用类型下土壤CA活性总体呈现出随植物根系深度增加而增加的变化趋势,从而说明土地利用类型是导致土壤碳酸酐酶剖面产生分异的主要因素,并为进一步研究土壤CA在自然界碳酸盐岩风化过程中的作用提供了科学依据。     

岩溶区和非岩溶区玉米光合作用与锌含量和碳酸酐酶关系的对比研究

采用田间试验方法对比研究岩溶区和非岩溶区玉米叶片光合作用与锌含量和碳酸酐酶活性的关系, 结果表明:岩溶区施加有机肥的土壤有效锌和玉米叶片锌含量均高于非岩溶区,岩溶区和非岩溶区的玉米叶片的锌含量分别为47.85 mg/kg 和43.35 mg/kg;岩溶区玉米叶片的碳酸酐酶活性和光合作用也高于非岩溶区,岩溶区的碳酸酐酶活性平均为5.622U,非岩溶区的碳酸酐酶活性平均为3.485U;碳酸酐酶活性随玉米叶片的锌含量增加而提高,而玉米光合作用效率随碳酸酐酶活性增加而提高,反映了土壤锌含量对玉米叶片锌含量、碳酸酐酶活性和光合作用的控制.     

The role of land use and environmental factors on microbial pollution of mountainous limestone aquifers

Limestone aquifers in Southern Italy are often affected by bacterial contamination produced by pasture and agriculture. The main goals of this study were (1) to analyze the role of land use and environmental factors on microbial contamination and, (2) to identify, at field scale, the most suitable indicator of fecal pollution, by comparing fecal coliforms and fecal enterococci. Analyzing surface and spring water, it was noted that both fecal indicators showed a significant decrease during the period characterized by freezing and/or freeze-thaw intervals. The data analysis shows that fecal coliforms are characterized by a significant decrease in population (3 orders of magnitude, at least) during the freezing period, while fecal enterococci are temporarily inhibited. A taxonomic classification of fecal enterococci detected in spring water samples was performed by the API 20 Strep system and by sequencing of the ribosomal 16S DNA genes. The results showed that freezing conditions did not cause any significant change on the set of enterococcal species.     

Effects of carbon anhydrase on utilization of bicarbonate in microalgae: a case study in Lake Hongfeng

A bidirectional labeling method was established to distinguish the proportions of HCO₃^? and CO₂ utilization pathways of microalgae in Lake Hongfeng. The method was based on microalgae cultured in a medium by adding equal concentrations of NaH¹³CO₃ with different δ¹³C values simultaneously. The inorganic carbon sources were quantified according to the stable carbon isotope composition in the treated microalgae. The effects of extracellular carbonic anhydrase (CAex) on the HCO₃^? and CO₂ utilization pathways were distinguished using acetazolamide, a potent membrane-impermeable carbonic anhydrase inhibitor. The results show utilization of the added HCO₃^? was only 8% of the total carbon sources in karst lake. The proportion of the HCO₃^? utilization pathway was 52% of total inorganic carbon assimilation. Therefore, in the natural water of the karst area, the microalgae used less bicarbonate that preexisted in the aqueous medium than CO₂ derived from the atmosphere. CAex increased the utilization of inorganic carbon from the atmosphere. The microalgae with CAex had greater carbon sequestration capacity in this karst area.     

The role of saline solution properties on porous limestone salt weathering by magnesium and sodium sulfates

Saline solution properties, viscosity in particular, are shown to be critical in salt weathering associated with sodium and magnesium sulfate crystallization in porous limestone. The crystallization of sodium and magnesium sulfate within a porous limestone has been studied at a macro- and microscale using different techniques, including mercury intrusion porosimetry, environmental scanning microscopy and X-ray computed tomography. Such analysis enabled the visualization of the crystallization process in situ, and at high magnification, yielding critical information as to where and how salts crystallize. Sodium sulfate decahydrate (mirabilite) tends to crystallize in large pores as euhedral micron-sized crystals formed at low supersaturation near to the surface of the stone. In contrast, magnesium sulfate heptahydrate (epsomite) tends to precipitate as anhedral wax-like aggregates formed at high supersaturation and distributed homogeneously throughout the stone pore system filling large and small pores. While the former crystallization behavior resulted in scale formation, the latter led to crack development throughout the bulk stone. Ultimately, the contrasting weathering behavior of the two sulfates is explained by considering differences in flow dynamics of solutions within porous materials that are mainly connected with the higher viscosity of magnesium sulfate saturated solution (7.27 cP) when compared with sodium sulfate saturated solution (1.83 cP). On the basis of such results, new ways to tackle salt weathering, particularly in the field of cultural heritage conservation, are discussed.     

Potentials of the microalgae inoculant in restoration of biological soil crusts to combat desertification

The world is presently faced to the many calamities, mainly the increased and rapidly developing environmental changes, soil degradation as an example of such environmental problems which is correlated with the destructive effects of the sandstorms. Biological soil crust (BSC), a main component of soil, has various environmental functions including reduction in the erosion by increasing soil stability and providing a sanctuary for the growth of the taxa and vascular plants communities. Destruction of BSC, which naturally can be recovered slowly in a long time processes, contributes to the desertification and other environmental catastrophes. Therefore, accelerating the BSC recovery both the quality and the quantity of the crust development, especially in the desert areas, is of the prime interest. Recent advances in the BSC restoration have provided an immense potential for emulating the natural restoration methods mainly through providing soils with inoculant. This paper reviews the present restoration-based procedures for the biological soil crust restoration practice. The main landmarks are presented and highlighted including strain(s) selection and development, mass biomass production, inoculum preparation, soil inoculation, soil augmentation, nurseries, and crust succession monitoring and control. The review also introduces several successful case studies in the USA and the Republic of China. Thereafter, the paper briefly documents the future directions of the research and technologies. Development of a restoration system through the application of the microalgae inoculant is an encouraging aspect for accelerating the BSC recovery of the arid and semi-arid areas. However, further researches will help to establish and consolidate the potential of the microalgae cells and their application in desertification programs in large scales and in accordance with principles and requirements mandated by economic standards.     

石灰岩裂隙摩擦强度愈合的压力溶解和应力腐蚀模型研究

为模拟试验中观察到的石灰岩裂隙摩擦强度愈合现象,提出用压力溶解和应力腐蚀相结合的综合模型来模拟裂隙摩擦强度的愈合。综合模型可同时考虑压力溶解和应力腐蚀对裂隙接触面的改造作用,通过裂隙接触面积的变化表征摩擦强度的愈合。模拟结果表明：压力溶解模型低估了短控制时间内摩擦强度的愈合量,通过进一步的参数敏感性分析发现,随着控制时间的增长,温度的升高显著地提高了压力溶解模型的模拟值,而有效应力的增加对模拟值的影响相对较小;应力腐蚀模型则主要反映应力压缩引起的裂隙接触面积增长;压力溶解模型和应力腐蚀模型结合则能较好地模拟裂隙摩擦强度的愈合。因此,用压力溶解模型模拟裂隙摩擦强度愈合时,特别是在模拟短控制时间内和低温条件下力学占主导作用的愈合时,应考虑应力腐蚀引起的裂隙接触面积变化。     

Occurrence of 3-hydroxy acids in microalgae and cyanobacteria and their geochemical significance

3-Hydroxy acids were detected in pure cultured microalgae: Chlorophyta—Chlamydomonas reinhardtii and Chlorella pyrenoidosa and Rhodophyta—Cyanidium caldarium (two strains), and cyanobacteria (Cyanophyta)—Anacystis nidulans, Phormidium foveolarum, Anabaena variabilis and Oscillatoria sp. Normal and branched (iso and anteiso) 3-hydroxy acids in the ranges of C₈-C₂₆ were found in all the samples studied at concentrations ranging from 0.036 to 2.3 and 0.000 to 0.12 mg g^?1 of dry sample, respectively. The major constituents were generally even-carbon numbered normal acids with carbon chain lengths below C₂₀. Microalgae and cyanobacteria may be the important sources of 3-hydroxy acids in natural environments.