我国几种土壤铁锰结核中的锰矿物类型

用Ｘ－射线衍射和化学选择溶提技术研究我国几种土壤中铁锰结核的锰矿物类型的结果表明：供试土壤铁锰结核都含有锂硬锰矿,除山东钙积潮湿变性以钙锰矿占优势外,其它样品中的锰矿物均以锂硬锰矿为主,结晶程度较高;湖北武汉和枣阳的粘磐湿润淋溶土的铁锰结核含有钠水锰矿和羟水锰矿;湖南宜章富铝湿润富铁土、湖北枣磐湿润淋溶土和山东钙积潮湿变性土的铁锰结核中的有钡硬锰矿;湖南桂阳富铝湿润富铁土的铁锰结核中检测出少量的铅     

土壤中铁锰结核微结构与组分研究进展

铁锰结核是土壤演化过程中形成的一种特殊新生体,其内部同心圆环带构造可用于反演古气候条件和成土环境,其组分可为微生物代谢提供营养元素和能量,进而影响土壤中养分和重金属的转化、固定与释放。本文综述了近几十年来国内外学者对土壤中铁锰结核研究所取得的进展,包括铁锰结核形成机制、演变过程与影响因素,不同地区铁锰结核微结构与组分差异,以及铁锰结核对养分转化与重金属吸附的影响。未来需进一步研究不同成土阶段铁锰结核形成速率与环境阈值,构建不同成土环境中铁锰结核演化模型,阐明铁锰结核对土壤中养分和重金属的固释机理,以期更好地理解地表关键带土壤发生过程与元素生物地球化学循环,为定量评价变化环境下土壤质量和功能提供依据。     

苏南水稻土对铜离子专性吸附的初步研究

六十年代以来,土壤对多价离子特别是重金属离子的专性吸附,已日益成为土壤化学领域中一个受人注意的问题。土壤胶体中铁、锰、铝、硅等氧化物及其水合物和土壤有机质是专性吸附的主要载体^{[12,16,17,19,20,21]},它们对许多重金属元素的专性吸附所引起的富集过程,起着控制这些金属元素在土壤溶液和海水中浓度的作用^[9,15,18];一些微盒营养元素在土壤中的移动及其对植物的有效性,也深受土壤中氧化物胶体的专性吸附的影响^[11,14,21]。因此,铁、锰等水合氧化物对重金属离子的专性吸附的研究,不仅是土壤化学领域,而且也是土壤环境保护和地球化学等领域中的重要研究课题。     

几种土壤锰结构对Cr（Ⅲ）的氧化与锰矿物类型

以几种土壤锰结核为实验材料，研究了不同氧化锰对Cr(Ⅲ）的氧化特性。结果表明，供试锰结核对Cr(Ⅲ）的氧化能力大小顺序为N1－1＞N4－1＞N2－1＞N5－1，与他们所含量还原性锰含量顺序不一致。换算的还原性锰对Cr(Ⅲ）的氧化后，则其顺序为N4－1＞N2－1＞N1－1＞N5－1。由组成供试锰结核的主要氧化锰矿物得知，对Cr(Ⅲ）的氧化能力：钠水锰矿＞锂硬锰矿＞钙锰矿。这可能与氧化锰矿物的结晶程度、晶体构造和Mn(Ⅳ）含量的差异以及Cr(Ⅲ）在氧化锰表面的吸附位置有关。     

金属离子在铁(氢)氧化物与腐殖质微界面上的吸附机理和模型研究进展

铁(氢)氧化物和腐殖质是广泛分布在土壤中的重要天然活性物质,因其具有较大的比表面积并且铁(氢)氧化物表面的-OH与腐殖质表面的-COOH、-OH等活性官能团可通过静电作用、配体交换等多种机制对重金属离子产生较强吸附,从而影响重金属离子在环境中的迁移、转化和生物效应。深入了解重金属离子在铁(氢)氧化物-腐殖质复合体微界面相互作用的分子机理,对于阐明重金属离子在环境中的迁移、转化过程具有重要意义。本文综述了金属离子在铁(氢)氧化物与腐殖质上吸附机理和模型的研究进展,为重金属污染土壤的风险评估和控制提供理论依据。     

不同氧化物硼负载体吸附锰离子的特性研究

以人工合成针铁矿（Goethite，简写为G），水锰矿（Manganite，简写为M），经硼砂处理的吸附态针铁矿（简写为Ad—B-G），吸附态水锰矿（简写为Ad—B-M），经硼酸处理的包被态针铁矿（简写为Oc—B—G），包被态水锰矿（简写为Oc-B—M）等6种氧化物为研究对象，在等温条件下，用吸附平衡法研究了6种硼负载体对Mn^2＋的吸附解吸行为。结果表明，吸附Mn^2＋能力：Oc—B—G〉Ad—B—G〉G；Ad—B—M和Oc—B—M吸附Mn^2＋量最大，M吸附能力最弱。6种硼负载体Mn^2＋吸附量随pH升高而增加,但铁氧化物和锰氧化物之间有差别。不同形态锰氧化物吸附Mn^2＋前后溶液pH变化不同，吸附等量Mn^2＋离子时，Ad—B—M向溶液中释放H^＋量最多，Oc—B—M最少。上述结果说明，硼的参与不仅可改变氧化物吸附Mn^2＋离子的行为，而且对反应体系的影响也不尽相同。     

低分子量有机还原性物质与土壤的相互作用 Ⅱ. 低分子量有机还原性物质与土壤作用的化学反应

论述了有机还原性物质与土壤作用的吸附、氧化还原和络合反应。土壤对该类物质的吸附量达加入量的60%～75%,其中强、弱还原性有机物质各约占1/2。负电荷物质的吸附量随土壤铁、锰氧化物及其所带负电荷量而变,并表现为电性吸附。对含—COOH、—C—NOH2功能团物质的吸附佐证了固相表面存在络合作用;在氧化-还原平衡中该类物质作为电子供体还原了铁、锰而自身被氧化;络合态亚铁、亚锰的形成服从络合-离解平衡,有机配位体的数量和H+离子争夺配位体的络合基可对其产生强烈的影响。     

几种土壤铁锰结核对Cr(Ⅲ)的氧化特性Ⅱ.pH、离子强度、温度等因素的影响

以我国几种土壤中铁锰结核为材料 ,研究了不同pH、离子强度和温度条件下氧化锰矿物对Cr(Ⅲ )的氧化。结果表明 :随着体系pH的降低、离子强度的增加以及温度的升高 ,供试铁锰结核对Cr(Ⅲ )的氧化量增加 ,这除了与其氧化还原反应本身消耗H 有关外 ,还与氧化锰矿物表面电荷性质和电位变化、共存的氧化铁矿物有关。而上述因素的变化导致N2 1、N4 1号样氧化Cr(Ⅲ )的增幅比N5 1号样的大 ,则可能与氧化锰矿物的结晶程度、晶体构造和铁锰结核中Mn(Ⅳ )的含量等有关     

土壤对重金属离子的竞争吸附

本文研究了理化性质不同的黄棕壤、红壤和砖红壤对Zn、Ni、Co的竞争吸附。采用含有不同重金属离子量的0.05molL^₁Ca(NO₃)₂溶液平衡,pH为5.5。结果表明,其吸附量的顺序:黄棕壤>砖红壤>红壤。对各离子的选择性为:Zn>Ni≥Co。竞争吸附的机制与非竞争吸附有明显的不同。其特征首先表现在吸附量上,竞争吸附要比非竞争吸附高得多。特别明显的,土壤去掉游离氧化铁后其吸附量不但不降,反而有不同程度的增加,Zn²⁺表现尤为突出;影响吸附量很大的陪伴阴离子作用受到严重抑制;反映土壤与重金属离子间作用能力大小的pH₅₀的变化符合吸附等温线的特点。其次根据土壤对重金属离子的吸附和解吸的情况,可以认为,红壤胶体表面吸附位数量远不及黄棕壤和砖红壤,但高能吸附位的比例高。     

含Ni六方水钠锰矿的表征及其对Pb 2+ (Zn2+)环境行为的影响

六方水钠锰矿是土壤中普遍存在、活性最强的氧化锰矿物。它常常富集各种过渡金属如Ni等,对其地球化学行为具有重要影响。在六方水钠锰矿形成过程中加入Ni2+,Ni以+2价存在于矿物中。进入水钠锰矿结构中的Ni大部分以[NiO6]八面体形式存在于层内;部分Ni存在于八面体空位上下方。含Ni水钠锰矿沿c轴方向堆叠锰氧八面体层数逐渐减小,而a-b板面晶体大小没有明显变化,即层片状晶体逐渐变薄,比表面积显著增大。随着Ni含量的增加,水钠锰矿结构中锰氧八面体空位数减少,而层边面吸附位点数基本保持不变,其对重金属离子(Pb2+/Zn2+)吸附去除能力逐渐降低。本文为明确过渡金属离子(Ni)对土壤中氧化锰矿物的形貌、结构及其性质的影响提供了参考。     

Observations on Manganese Deficiency and Toxicity in Some Australian Native Plants

Analysis and research on the nutrition of some Australian native plants as well as diagnostic analysis of failed native plant gardens reinforces the view that manganese (Mn) availability is a major factor in the edaphology and cultivation of Australian native species. Yellow Kandosol soils on sandstone show a unique endemic floral assemblage. These soils show low total soil Mn levels of only 20–30 mg/kg. Despite this, endemic species such as Eucalyptus haemastoma and Acacia suaveolens show greater foliar Mn levels (around 291 and 389 mg/kg, respectively) than iron (Fe) levels, with Fe/Mn ratios as low as 0.14 and 0.27. During pot trial work on artificial soils created from crushed sandstone and green waste compost that were designed to research phosphorus (P) and calcium (Ca) nutrition, some interesting data on Mn uptake were collected. Levels of foliar Mn as high as 1250 and 389 mg/kg, respectively, accumulated in E. haemastoma and A. suaveolens when soils were artificially acidified to pH 4.7 (CaCl₂) using ferrous sulfate. These Mn levels were associated with visible toxicity symptoms in foliage of E. haemastoma but not in A. suaveolens. Foliar Mn in both species showed a strong inverse correlation (R² > 0.93) with soil pH. Previous research has shown that eucalypts from this floral assemblage are prone to Mn toxicity when grown in conditions of high soil Mn availability. Diagnostic analysis of soils and foliage for a client with horticultural problems in a native plant landscape showed severe chlorosis in a wide range of native species due to Mn deficiency induced by neutral soil pH (around 7.0 in CaCl₂). Such soil pHs are considerably greater than those of the plant’s natural distribution. Despite apparently elevated soil P and the appearance of what looked like P toxicity, foliar P levels were not sufficiently elevated to conclude acute P toxicity but rather simple and severe Mn deficiency. The work suggests that induced Mn deficiency and toxicity may be underdiagnosed problems in the cultivation of many Australian native plants.     

Forms and Uptake of Manganese in Relation to Soil Taxonomic Orders in Alluvial Soils of Punjab,India

Different forms of manganese (Mn) were investigated, including total, diethylenetriamine penta-acetic acid (DTPA) extractable, soil solution plus exchangeable (Mn), Mn adsorbed onto inorganic sites, Mn bound by organic sites, and Mn adsorbed onto oxide surfaces, from four soil taxonomic orders in northwestern India. The total Mn content was 200–950 mg kg^?1, DTPA-extractable Mn content was 0.60–5.80 mg kg^?1, soil solution plus exchangeable Mn content was 0.02–0.80 mg kg^?1, Mn adsorbed onto inorganic sites was 2.46–90 mg kg^?1, and Mc adsorbed onto oxide surfaces was 6.0–225.0 mg kg^?1. Irrespective of the different fractions of Mn their content was generally greater in the fine-textured Alfisols and Inceptisols than in coarse-textured Entisols and Aridisols. The proportion of the Mn fractions extracted from the soil was in the order as follows: Adsorbed onto oxide surfaces > adsorbed onto inorganic site > organically bound > DTPA > soil solution + exchangeable. Based on coefficient of correlation, the soil solution plus exchangeable Mn, held onto organic site and oxide surface (amorphous) and DTPA-extractable Mn, increased with increase in organic carbon of the soil. The two forms, adsorbed onto inorganic site (crystalline) and DTPA extractable, along with organic carbon, increased with increase in clay content of the soil. DTPA-Mn and Mn adsorbed onto oxide surfaces and held on organic site decreased with increased with an increase in calcium carbonate and pH. Total Mn was strongly correlated with organic carbon and clay content of soil. Among the forms, Mn held on the organic site, water soluble + exchangeable and adsorbed onto oxide surface were positively correlated with DTPA-extractable Mn. DTPA-extractable Mn seems to be a good index of Mn availability in soils and this form is helpful for correction of Mn deficiency in the soils of the region. The uptake of Mn was greater in fine-textured Inceptisols and Alfisols than in coarse-textured Entisols and Aridisols. Among the different forms only DTPA-extractable Mn was positively correlated with total uptake of Mn. Among soil properties Mn uptake was only significantly affected by pH of the soil.     

腐殖质对白浆土中Fe、Mn、Al形态转化及磷生物有效性的影响

在三江平原布置长期试验，研究连年施用有机肥后土壤腐殖质变化及其对白浆±Fe、Mn、Al形态转化及磷生物有效性的影响。结果表明，施用牛粪后土壤腐殖质含量升高，且以松结态腐殖质的增长为主；土壤的DTPA提取态和有机络合态Fe、Mn、Al含量上升，使土壤有效态磷含量上升。因此，生物措施是治理白浆土，促进土壤磷素养分有效性上升，增大土壤缓冲容量和抗逆性的有效措施。     

腐殖质对白浆土中Fe、Mn、Al形态转化及磷生物有效性的影响

在三江平原布置长期试验，研究连年施用有机肥后土壤腐殖质变化及其对白浆±Fe、Mn、Al形态转化及磷生物有效性的影响。结果表明，施用牛粪后土壤腐殖质含量升高，且以松结态腐殖质的增长为主；土壤的DTPA提取态和有机络合态Fe、Mn、Al含量上升，使土壤有效态磷含量上升。因此，生物措施是治理白浆土，促进土壤磷素养分有效性上升，增大土壤缓冲容量和抗逆性的有效措施。     

Ammonium‐driven nitrification plays a key role in increasing Mn availability in calcareous soils

Background : Manganese deficiency often becomes a yield limiting factor, particularly on calcareous soils, even though the total soil manganese content is usually sufficient. Although it is known that acidifying N fertilizers can improve Mn availability, the reason of this effect is still unknown. Aim : Our aim was to investigate the effect of stabilized ammonium fertilizers as a tool to distinguish between physiological‐ and nitrification‐induced acidification. Method : Two pot experiments with Triticum aestivum L. and one soil incubation experiment using different nitrogen forms (CN = calcium nitrate, AN = ammonium nitrate, AS = ammonium sulfate, ATS = ammonium thiosulfate) with and without addition of nitrification inhibitors (DCD, Nitrapyrin, Piadin, DMPP) were conducted to examine the effect on Mn availability in the soil and Mn uptake by the plants at different development stages (EC 31 und 39). Results : With increasing fertilizer ${\mathrm{NH}}_4^{+}$ content a higher Mn concentration was detected: CN: 32 µg Mn g^?1 DM, AN: 39 µg Mn g^?1 DW, AS: 55 µg Mn g^?1 DM, ATS: 109 µg Mn g^?1 DM. The addition of a nitrification inhibitor resulted in a significantly lower rhizosphere pH compared to the non‐stabilized fertilizer. Surprisingly, the use of different nitrification inhibitors led to unchanged (CN, AN) or lower Mn concentrations of wheat. Especially in the ${\mathrm{NH}}_4^{+}$ treatments (AS and ATS), this negative effect was very evident (AS+DCD: 42 µg Mn g^?1 DM; ATS+DCD: 55 µg Mn g^?1 DM). Conclusions : Mn availability was enhanced by ongoing nitrification process rather than physiological acidification. Compared to other N forms, ammonium thiosulfate led to the highest Mn availability in bulk soil.     

种植制度和施肥对半干旱区土壤中锰形态及有效性的影响

Manganese(Mn) deficiencies are common in soils on the Loess Plateau of China. This research provided essential information on improving Mn availability in semiarid soils through agricultural practices. Twelve cropping system and fertilization treatments were designed in a 28-year experiment. The cropping systems included long-term fallow, continuous winter wheat cropping, pea(1 year)-winter wheat(2 years)-millet(1 year) rotation(crop-legume rotation) cropping, and continuous alfalfa cropping. The fertilizer treatments under the cropping systems included no-fertilizer control(CK), application of P fertilizer(P), application of N and P fertilizers(NP), and application of N and P fertilizers and manure(NPM), but the NP treatment was excluded in the continuous alfalfa cropping system. Available Mn and Mn fractions of soil samples(0–20 and 20–40 cm depths) were measured and further analyzed quantitatively using path analyses. Results showed that the crop-legume rotation and continuous alfalfa cropping systems significantly increased available Mn compared with the fallow soil. Compared with the no-fertilizer control, manure application increased available Mn in soil of the continuous wheat cropping system. Across all treatments, the averaged content of mineral-, oxide-, carbonateand organic matter-bound and exchangeable Mn accounted for 42.08%, 38.59%, 10.05%, 4.59%, and 0.09% of the total Mn in soil,respectively. Cropping significantly increased exchangeable Mn in soil and the highest increase was 185.7% in the continuous wheat cropping system at 0–20 cm depth, compared with the fallow soil. Fertilization generally increased exchangeable and carbonate-bound Mn in soil. Carbonate-bound Mn was the main and direct source of available Mn in soil, followed by exchangeable and organic matterbound Mn. These results indicated that crop-legume rotation cropping, continuous alfalfa cropping and application of manure, have the potential to promote Mn availability in soils of rainfed farmlands.     

Manganese uptake and Mn efficiency of wheat cultivars are related to Mn‐uptake kinetics and root growth

Wheat cultivars differ widely in manganese (Mn) efficiency. To investigate the reasons for different Mn efficiencies, a pot experiment with soil, a solution‐culture experiment, and model calculations were carried out. The pot experiment was conducted with wheat (Triticum aestivum L. cvs. PBW 373, PBW 154, PBW 343, PBW 138, and Triticum durum L. cvs. PBW 34 and PDW 233) grown in a screen house in India. The soil was a loamy sand with pH 8.1, DTPA‐extractable Mn 1.62 mg (kg soil)^–1, and initial soil solution Mn concentration (C_Li) of 0.19 μM. When fertilized with 50 mg Mn (kg soil)^–1, C_Li increased to 0.32 μM. At C_Li 0.19 μM, wheat cv. PBW 373 produced 74% of its maximum shoot dry weight (SDW) with 64% of its maximum root length (RL), while cv. PDW 233 produced only 25% of its maximum SDW with 11% of its maximum RL. The other wheat cultivars were between these extremes. Manganese deficiency caused a reduction in shoot growth, but more strongly reduced root growth. The low Mn efficiency of T. durum cv. PDW 233 was related to a strong depression of its root growth. Manganese influx was similar for all cultivars. In solution culture below 1 μM Mn, under controlled climate‐chamber conditions, Mn influx was linearly related to Mn concentration. Both the efficient cv. PBW 343 and the inefficient cv. PDW 233 had a similar influx. Uptake kinetic parameters from the solution experiment together with soil and plant parameters from the pot experiment were used in a mechanistic nutrient‐uptake model. Calculated values of Mn influx for wheat grown in soil were 55% to 74% of measured values. A sensitivity analysis showed that increasing C_Li or the slope of the uptake isotherm by about 30% would be enough to reach the observed influx. The results of this research indicate that an increase of Mn solubility by microbial or chemical mobilization would increase Mn uptake. But on the other hand, no chemical mobilization would be required to increase Mn uptake if the plant improved its uptake kinetics. Low Mn efficiency of some wheat cultivars was related to their reduced root growth at low soil Mn supply.     

不同供锰量对小麦生理生化的反应研究

溶液培养试验研究缺Mn、低Mn和正常供Mn对小麦生长发育的影响结果表明 ,缺Mn与低Mn均使敏感品种“京冬 8号”生长量显著降低 ,NO3- N和可溶性蛋白质含量显著增加 ,而氨基酸含量除供Mn 0 0 0 1 μmol L处理显著降低外 ,其他处理间均无明显差异 ,各项指标均表现为低Mn比缺Mn影响更大 ,蛋白质电泳中低Mn较缺Mn以及其他处理缺失了 2条蛋白质带。且敏感品种“京冬 8号”比抗病品种“临远 70 6 9”表现更明显     

Contribution of Post-Anthesis Growth and Manganese Dynamics to Differential Grain Yield in Different Wheat Species

Manganese (Mn) deficiency has become a serious nutritional problem for wheat grown in alkaline coarse textured soil. The study aimed to investigate post-anthesis Mn partitioning in different wheat species. Cultivars of bread wheat (‘PBW509’, ‘DBW17’, ‘PBW550’ and ‘PBW636’); durum wheat (‘PDW291’) and triticale (‘TL2908’) were grown in 6.5 L pots with two treatments of Mn (0 and 50 mg Mn kg^?1 soil) in screen house and harvested at anthesis, 18- days post-anthesis, and maturity to record Mn uptake. Durum cv. ‘PDW291’ retained highest proportion of Mn in its vegetative parts under Mn deficiency resulting into lowest partitioning to the grain and had the lowest grain yield. All bread wheat cv. facilitated superior Mn partitioning to the grain, lesser retention in vegetative organs and higher Mn utilization efficiency, than triticale and durum wheat species. Cultivars producing higher yield on Mn deficit soils are viable alternative to foliar application of Mn.