原位直接成像法在研究黑云母溶解过程中的应用

采用原位直接成像法(In situ atomic force microscopy)研究层状硅酸盐含钾矿物黑云母与低分子量有机酸的界面反应。结果表明,在近分子尺度下,黑云母具有典型的层状结构单元,高度约1 nm。天然黑云母片(001)面并非完全解理,其上既有台阶也有残片、碎片和蚀坑。在pH 6.0的柠檬酸盐溶液作用下,0~45 min内,黑云母(001)面上的台阶以0.01μm2min-1的恒定速率溶解,之后溶解速率降低;表面原有蚀坑边缘变模糊,但面积没有明显变化,同时(001)面上也没有新的蚀坑形成。通入pH 4.0柠檬酸盐溶液,经过89 min的反应,大量无规则形状的蚀坑产生并散乱分布于(001)面上,深度以0.7~1.1 nm为主;另外表面上还有诸多微型蚀坑正在形成并逐渐扩展为较大的蚀坑。结合水-矿物界面反应理论可知,弱酸环境条件下,黑云母溶解从表面的缺陷/扭折位点开始,以单层(TOT)溶解为主,沿着[hk0]方向发展并伴随着层间K和晶格中Si、Al、Mg和Fe的释放。本研究结果表明原位直接成像技术能够弥补常温常压条件下宏观研究技术的不足、通过可视化来实时表征层状硅酸盐矿物-水溶液的界面反应过程。另外,原子力显微镜技术对其他领域的界面研究同样具有较高的借鉴意义。     

腐殖酸在黑云母表面的吸附动态和分布特征研究

采用原位原子力显微镜智能模式初步观察了弱酸性土壤腐殖酸分子在层状硅酸盐含钾矿物黑云母表面的吸附动态和形貌变化。采用纯化、干燥后的腐殖酸固体样品配制p H 6.0,浓度分别为0 mg L-1、100 mg L-1和1000 mg L-1的腐殖酸溶液。原位观察所用的矿物薄片为土壤中常见的2∶1型含钾矿物—黑云母,其化学结构式为K(Mg2.46Fe0.45Ti0.09)[Al Si3O10](OH)2。结果表明,时间尺度是影响界面上腐殖酸形貌结构的一个重要因素。在通入p H 6.0的腐殖酸溶液作用下,原位反应0~180min内,腐殖酸分子与黑云母(001)面的相互作用以吸附为主并伴随脱附现象,吸附的腐殖酸呈球状,为单个或多个腐殖酸分子的聚集体,高度介于1~5 nm之间;原位反应180~300 min内,黑云母(001)面上吸附的腐殖酸仍以颗粒态为主,高度介于3~5 nm之间,平均为4 nm;而黑云母(001)面上的台阶和边缘位置则分布有较多的片状结构以及黑云母线型边缘诱导产生的链状结构腐殖酸聚集体,其高度介于6~8 nm,较颗粒态腐殖酸的聚集体平均高出约2.5 nm。此外,腐殖酸分子不仅能够在黑云母表面进行吸附和脱附作用,还能够溶解黑云母的表面结构,促进层间K及结构单元内Al和Si的释放。因此,腐殖酸与云母类矿物的界面反应是一个溶解—吸附—聚集并伴随着脱附和离子释放的过程。     

柠檬酸对高岭石的溶解作用

采用间歇法(batch method)研究柠檬酸对高岭石溶解的影响。结果表明:低浓度(0.02mmolL-1)柠檬酸可促进高岭石中Ca2+、Mg2+、Na+少量的释放。当柠檬酸浓度分别为1.0mmolL-1和8mmolL-1时,Ca2+,Mg2+,K+,Na+,Si,Al3+阳离子的释放量也相应地增加。释放的Ca2+、Mg2+主要来自高岭石表面的吸附,而Na+、K+则来自高岭石的溶解。     

柠檬酸/柠檬酸盐对暗棕壤磷的释放效应及机制

模拟森林凋落物淋洗液中柠檬酸/柠檬酸盐浓度范围,设计了不同浓度柠檬酸/柠檬酸盐一次性和多次连续浸提系列实验,柠檬酸(阴离子)载荷量为0~200 mmol/kg。结果表明,柠檬酸/柠檬酸盐显著促进A1层暗棕壤磷的活化释放,磷释放量随浓度升高大致呈线性增加,但B层释放效应较弱。pH5.16柠檬酸盐解磷效率高于同浓度柠檬酸,因此推断,凋落物中柠檬酸(盐)促进暗棕壤磷释放的主要机理在于柠檬酸阴离子反应。柠檬酸盐对暗棕壤磷的释放具有一定的累加性,磷释放量主要由柠檬酸阴离子累积载荷量决定,而与其加入方式关系不大;柠檬酸盐加入时,磷释放量Y(mg/kg)与柠檬酸阴离子累积载荷量X(mmol/kg)间回归方程为Y=-0.0011X2 0.5187X-0.1391,R2=0.9980。仅以凋落物层溶出柠檬酸量进行估计,由此增加的A1层暗棕壤磷释放量为0.32 kg/(hm2.a),约相当于中龄林年吸收磷量的1/23~1/36,其实际作用不可忽视。     

柠檬酸和葡萄糖存在下土壤锰溶解动力学研究

研究探讨了土壤锰还原和溶解的动力学特征,为土壤锰的植物有效性提供科学依据。以无机酸和酸化还原剂(HCl、NH2OH.HCl-HNO3、NH2OH.HCl-HAc)处理为对照,用连续液流法研究柠檬酸和葡萄糖对土壤锰溶解的影响。结果表明,柠檬酸、葡萄糖可通过在土壤固相表面的吸附使其中的锰还原溶解,几种化合物对土壤锰的相对溶解能力强弱顺序为:0.04 mol.L-1NH2OH.HCl(25%HAc)>0.1 mol.L-1NH2OH.HCl-0.001 mol.L-1HNO3>1%柠檬酸>0.5%柠檬酸>0.1 mol.L-1HCl>1%葡萄糖>0.5%葡萄糖>0.01 mol.L-1HCl。用不同数学模型模拟化合物对土壤锰溶解动态过程,5种方程拟合的相关系数均达到极显著水平(P<0.01),并且以指数方程、Elovich方程和权函数方程拟合所得的标准差较小,抛物线扩散方程拟合的标准差最大。表明几种化合物对土壤锰氧化物的溶解速率受控于表面化学反应,而不是由扩散来控制。     

砾石含量对土壤可蚀性因子估算的影响

砾石(2 mm)是土壤组成部分之一,其含量对侵蚀产沙有重要影响。在土壤可蚀性因子(K)计算中充分考虑砾石含量的影响,计算所得土壤可蚀性因子会更加准确。利用30弧秒分辨率土壤砾石含量和土壤质地等级等数据,利用文献报道的砾石含量与土壤渗透性和土壤侵蚀关系估算方法,在全球范围内分析估算砾石含量对土壤可蚀性因子的影响。结果表明,(1)土壤剖面中砾石的存在,通过降低土壤入渗速率(土壤渗透性等级增加5.68%)、增加地表径流而使土壤侵蚀增加,进而使全球土壤可蚀性因子增加4.43%;砾石覆盖通过保护土壤免遭雨滴打击和径流冲刷减少侵蚀,在山地、荒漠(沙漠和戈壁)地区,这一影响会使土壤可蚀性值减小约18.7%。考虑土壤剖面砾石含量和表面砾石覆盖综合影响时,土壤可蚀性因子降低5.52%。(2)以砾石影响为主的地区,占全球62.7%,土壤可蚀性因子可降低0.0091(t·hm~2·h)·(hm-2·MJ~(-1)·mm~(-1));以剖面砾石影响为主的地区,占全球的31.1%,土壤可蚀性因子增加0.0019(t·hm~2·h)·(hm-2·MJ~(-1)·mm~(-1))。(3)剖面和表面砾石共同作用使6个样区土壤流失速率减少约11.8%。因此,剖面砾石的存在会增加土壤可蚀性,而表面砾石覆盖会减少土壤可蚀性,综合影响使土壤侵蚀降低。在区域土壤可蚀性制图研究中,应考虑这两个方面的影响,进而提高土壤可蚀性因子的制图精度。     

模拟降雨条件下塿土的溅蚀特征试验研究

溅蚀在破坏土壤表层结构的同时为后续侵蚀提供丰富材料,以黄土高原典型土壤塿土为试验用土,通过模拟降雨试验,根据溅蚀速率、溅蚀前后土壤颗粒组成及表面强度变化指标,系统研究塿土的溅蚀特征。结果表明,溅蚀速率随降雨历时呈现幂函数变化,分为迅速降低、缓慢降低、趋于稳定3个阶段。土盘表面松散颗粒及利于溅蚀的粒级范围内颗粒的消耗、团聚体破碎及超渗产生的水层消耗雨滴能量、结皮的形成和发育分别是3个阶段的主要影响因素。在90mm/h的雨强下,塿土颗粒富集与耗损的临界粒径是0.05mm,雨滴打击分离粒级0.05mm颗粒,富集迁移粒级0.05mm颗粒。当含水率相等时,降雨历时越长贯入深度越浅。塿土表面强度随降雨历时增加,0~30min是塿土结皮形成的关键时期。塿土溅蚀过程是表土颗粒组成不断变化和表面强度逐渐完善的过程。     

铝胁迫下大豆根系脱落酸累积与柠檬酸分泌的关系研究

为探讨铝(Al)胁迫条件下脱落酸(ABA)调控植物根系有机酸分泌的机制,进行了ABA与Al诱导大豆根系柠檬酸分泌的关系试验。结果表明:1)外源ABA和ABA合成抑制剂fluridone分别提高和降低了Al诱导的大豆根尖ABA含量的增加,但对根系柠檬酸分泌量均无影响,ABA对根系内源柠檬酸含量和柠檬酸合成酶的活性也没有影响;2)分根试验表明,与Al直接接触的根部(Part A)内源ABA含量发生变化,且有柠檬酸的分泌,而不与Al直接接触的根部(Part B)内源ABA含量也发生变化,但没有柠檬酸分泌;3)Al胁迫下,大豆耐Al基因型柠檬酸分泌量远高于敏感基因型,但二者的内源ABA含量却没有差异;4)30μmol AlCl3处理,在0~12 h柠檬酸分泌速率和内源ABA含量随Al处理时间增加而增加,去除Al胁迫时(12~18 h),柠檬酸分泌速率继续增加,但内源ABA含量则迅速下降。综合以上结果,推测ABA不是通过提高Al诱导柠檬酸分泌来调控大豆耐Al性。     

添加葡萄糖对不同深度红壤碳矿化及其温度敏感性的影响

土壤碳矿化速率及温度敏感性是研究陆地生态系统碳循环的重要指标,以往研究多集中在表层土壤,但不同深度土壤属性及碳质量具有显著的差异。以亚热带马尾松/木荷人工混交林红壤为研究对象,选择0~10 cm、10~30 cm、30~60 cm和60~100 cm四种深度土壤,设置葡萄糖添加(G+)和空白对照(CK)两组处理,进行周期性变温(4、14、22和30℃)培养,并利用自主研发设备测定第1、3、7、14、21和28天5~30℃模拟昼夜周期性变温条件下的土壤碳矿化速率,研究添加葡萄糖对不同红壤碳矿化速率及其温度敏感性(Q10)的影响。结果表明:无葡萄糖添加时,随着土壤深度和培养时间增加,土壤碳矿化速率显著降低,但Q10无显著差别,培养后期底物供给不足限制了土壤碳矿化速率。葡萄糖添加后,随着土壤深度增加,土壤碳矿化速率及Q10均显著增加,浅层土壤响应较快,深层土壤响应慢但增幅更大。培养末期深层土壤碳矿化速率甚至高于表层土壤。不同深度土壤微生物含量及其群落结构组成是土壤碳矿化速率及其Q10响应差异的主要影响因素。     

蒙脱石纳米颗粒聚集中的离子特异性效应

原子力显微镜(AFM)是一种研究颗粒聚集与黏附力比较直观的显微工具。运用原子力显微镜观察测定了几种碱金属氯化盐溶液处理的蒙脱石颗粒在风干条件下的形貌图和黏附力。结果发现,蒙脱石颗粒聚集存在明显的离子特异性效应。在50 mmol L~(-1)的高浓度条件下,CsCl体系中蒙脱石颗粒聚集的高度、直径以及针尖与颗粒的黏附力均存在离子特异性效应,其序列满足LiClNaClKClRbClCsCl。在10 mmol L~(-1)的低浓度条件下,除Cs~+处理蒙脱石高度为2~10 nm,其余高度均为1~2 nm的单粒,离子特异性效应不明显。影响颗粒聚集中的离子特异性效应的主要因素为离子体积和量子涨落效应,在低浓度下量子涨落和体积效应作用弱,因此聚集行为差异不明显;在高浓度下离子体积和量子涨落贡献大,导致了不同离子体系下颗粒聚集体以及与针尖的黏附力差异增大。     

四种常规方法提取伊利石有效钾的机制比较

采用化学分析、X射线衍射、中红外光声光谱以及原子力显微镜的方法,比较了0.2 mol L~(-1)四苯硼钠法、1 mol L~(-1)沸硝酸法、2 mol L~(-1)冷硝酸法和2 mol L~(-1)热盐酸法浸提伊利石中有效钾的机制。结果表明,四苯硼钠法浸提时,伊利石中钾素释放量达到全钾量的59.5%,且基本均通过层间交换反应予以释放,结构离子铁、铝和硅释放量极低;采用三种酸溶液浸提时,其钾素释放量仅占全钾量的1.53%~2.46%,通过层间交换反应释放的钾量占释放量的比例为88.4%~94.0%。四苯硼钠浸提时伊利石层间距扩大,产生次生过渡矿物,并形成富硅表层,但在伊利石表面无溶蚀特征;三种酸溶液浸提时伊利石结构无改变,但其结晶度降低,且表面有明显的溶蚀特征。因此,土壤矿物层间钾是作物可利用有效钾的主要来源,三种酸溶液浸提方法一方面低估了有效钾容量,另一方面提取了一部分不能为植物所利用的结构态钾,不适宜于用来评价伊利石及土壤有效钾库容量。     

Surface morphology of quartz grains from tropical soils and its significance for assessing soil weathering

The surface morphology of quartz grains can indicate the degree of weathering of soil material. We have compared two methods of assessing the relative weathering of soils on the basis of differences in the surface morphology of quartz sand grains in a catena of soils in Rwanda. One method is based on the presence or absence of surface features indicative of weathering or freshness, while the other uses the frequency and size of dissolution etch pits. A ranking of relative weathering could be obtained using the first technique for the slightly and somewhat weathered soils but not for the weathered soils. On the other hand, weathering trends and differences between the horizons studied were detected in weathered soils using the second method. The introduction of more specific definitions of the weathering classes used in the latter method leads to clear improvement of the inter-observer reproducibility of the weathering classification. The surface features on the quartz grains suggest that the soil at the summit is less weathered than the other soils of the sequence. Quartz grains from the well-drained soils on the slopes, which are subjected to more intense leaching and thus to stronger chemical weathering, have more triangular etch pits and chatter marks. In the imperfectly drained soils in the valley bottom quartz grains are less etched because dissolution is inhibited by the oversaturation in silica of the drainage waters.     

The use of quartz grain microtextures in the study of the origin of sand terrains in Western Australia

The origin of extensive sand terrains which lie inland from the coastal margin of Western Australia is contentious, with the debate centering around an in situ vs. an aeolian origin. To resolve this debate the shape and surface features of sand grains are reported for sandplains, sand dunes and bedrock for the Victoria Plateau sandplain, which lies in the central west coastal region of Western Australia. All three components of the Victoria Plateau are similar in grain shape and microtexture. Quartz grains show a combination of chemical dissolution and precipitation micromorphology. Characteristics of dissolution include etch patterning, triangular shaped etch pits and solution features. Precipitation forms include edge rounding, silica veneers and plate- and sheet-like structures. Features such as peeling plates, complex precipitation forms projecting from grain surfaces, adhering particles and preserved grain contact faces indicate stability rather than a transport dominated environmental history. The combination of preserved dissolution and precipitation forms, a dearth of mechanically derived features and a correspondence between grains in rock and overlying sands points to local siliceous sedimentary rocks as the source of the sands.     

Biotite weathering by <Emphasis Type="Italic">Aspergillus niger</Emphasis> and its potential utilisation

Purpose

Biotite, as a type of associated mineral, is normally applied as a filling material for buildings, or is discarded as tailings. However, as a potassium-bearing phyllosilicate mineral, biotite can be easily weathered by fungi, which leads to its internal potassium being released for agricultural production (1), and the mineral residues being weathered by the fungus may be applied for adsorption of heavy metal ions (2).

Materials and methods

This work investigates the weathering of biotite by Aspergillus niger through the analysis of the differences in ion dissolution from biotite, producing of organic acids, the change of mineral morphology and composition by inductively coupled plasma optical emission spectrometry (ICP-OES), high-performance liquid chromatography (HPLC), scanning electron microscopy (SEM), and X-ray diffraction (XRD). Besides, the mineral residues were applied for adsorption of heavy metal ions.

Results and discussion

Results showed that the mycelia envelope the mineral and form fungal–mineral aggregates. The fungus can secrete a variety of organic acids including citric acid and oxalic acid; these attacked the surface and cleavage of biotite to release ions (Al³⁺, Fe³⁺, Mg²⁺, and K⁺). During incubation with A. niger, biotite weathered as shown by the relative decrease in biotite content and increase in interlayer spacing. Moreover, a certain concentration of phytic acid and tween-80 could promote the release of K⁺, and the fermentation liquid of rice bran has the same effect. Biotite residues showed a good adsorption for Cd²⁺, Pb²⁺, Zn²⁺, and Cu²⁺.

Conclusions

The results indicate that biotite can be biotransformed and release K⁺, of which the production can be acted as heavy metal ion adsorbent. It provides a reference for application of biotite in agriculture and control of heavy metal ion pollution in soil.

     

不同培肥处理对土壤溶解性有机碳含量及特性的影响

以黄土高原南部地区的长期肥料定位试验为研究对象,通过室内测定及培养试验研究了不施肥(CK)、撂荒(FA)、施氮磷钾肥(NPK)、氮磷钾配施有机肥(MNPK)和氮磷钾配施秸秆(SNPK)培肥处理土壤中溶解性有机碳(DOC)的含量、结构特性及其降解特性。结果表明,在0～20 cm耕层土壤中,不同培肥处理土壤中DOC的含量变化范围在4.65～8.94 mg kg-1之间,平均为6.42 mg kg-1,各培肥处理间差异明显,其大小顺序为MNPKSNPKNPKFACK。由DOC溶液的UV280吸收值和腐殖化指数(HIXem)可以得出,不同培肥处理土壤中溶解性有机物中结构相对复杂的芳香化合物所占的比例明显不同,其大小顺序为SNPKMNPKFANPKCK。经过7d的生物降解培养,不同培肥处理土壤DOC溶液的降解率变化范围在19.3%～48.5%之间,平均为28.6%,其大小顺序为CKFANPKSNPKMNPK。随着培养的进行,DOC溶液中结构较为复杂的溶解性有机物的比例上升。     

喀斯特森林植被自然恢复过程中土壤有机碳库特征演化

采用空间代替时间的方法,研究了茂兰喀斯特森林自然恢复过程中土壤有机碳库特征,结果表明:土壤容重(0～10 cm土层0.94～1.15 g cm-3,＞30 cm土层0.98～1.19 g cm-3)、石砾含量(0～10 cm土层19.93 ～26.61％,＞30 cm土层20.36 ～32.11％)随恢复进展而减少,随土层加深而增加;土壤容积(0～10 cm土层20.13 ～22.02 m3,＞30 cm土层4.16～6.87 m3)、有机碳含量(0 ～10 cm土层21.14 ～52.67 g kg-1,＞ 30 cm土层11.15 ～25.93 g kg-1)、有机碳密度[(0 ～ 10 cm土层1.91 ～4.03 kg m-2,＞ 30 cm土层0.39～1.96 kgm-2)、有机碳储量(900 m2样地0 ～ 10 cm土层0.538 ～0.883 t,＞30 cm土层0.039 ～0.137 t)、易氧化碳含量(0～10 cm土层5.28 ～33.25 g kg-1,＞ 30 cm土层5.98 ～ 14.13 g kg-1)均随恢复进展而增加,随土层加深而减少;随恢复进展0 ～ 20 cm土层有机碳稳定性增强、活性降低,＞20 cm土层则相反;随土层加深有机碳稳定性增强、活性降低;土壤有机碳随恢复进展总体上具碳汇效应,且早期其量少质低、表聚性强、碳汇效应不显著、固碳潜力大,后期则相反.加强保护喀斯特森林,使其自然恢复,有利于土壤质量的提高和有机碳的累积.     

THE STABILITY OF DICALCIUM PHOSPHATE DIHYDRATE IN SOIL

The rate of dissolution of dicalcium phosphate dihydrate (DCP) when incorporated in moist soil was investigated using ³²P. The moisture content of the DCP-soil mixture, the surface area of the DCP particles and the temperature of incubation of the system are all directly related to the rate of dissolution of the DCP. These results may be explained using a diffusion model in which phosphate ions diffuse from a water film adjacent to the DCP towards a sink provided by the soil.     

坡面薄层含沙水流水动力学参数提取的方法

针对坡面径流水深浅(1～5mm)和水动力学参数(流速、水深等)提取困难,给坡面侵蚀径流水流结构、能量耗散及泥沙输移等的深入研究带来困难的问题,基于水动力学原理和相似性理论,通过"非常规比尺模型"将径流水深进行放大,来研究坡面薄层含沙水流的水流相似过程。结果表明:(1)当薄层含沙水流水深放大2.5倍,含沙量在10～320kg/m~3时,薄层含沙水流原型和模型的水面线(阻力)、流速、侵蚀地形的误差分别为0～0.1%,0.1%～5.3%,0.9%～4.9%,误差均在允许范围之内,原型和模型满足几何、运动等相似比尺转换关系;(2)水深在0.5～1.25cm时,薄层含沙水流为紊流,原型和模型的流速垂向分布满足对数分布,可以用同一方程进行表达;(3)"非常规比尺模型"可以作为一种方法应用到薄层含沙水流的水动力学参数提取、水流结构、能量耗散、泥沙输移等的深入研究过程中。     

The effects of chemical weathering on the morphology and strength of quartz grains–an example from S.W. Australia

In soils in south-western Australia rounded quartz pebbles and sand grains have been greatly modified by chemical dissolution. Evidence of dissolution was provided by thin sections, scanning electron microscopy and measurements of quartz grain strength. Dissolution is initiated at fractures and intercrystalline boundaries so that dissolution along intersecting microfractures produces various surface etch features including tessellated pyramidal surface textures. The alteration of quartz grains by dissolution prevents the use of quartz as a stable reference mineral in studies of pedogenesis in these soils.