酸和氧化还原剂对二氧化锰溶解度的影响

由于土壤中锰的有效性随pH和Eh的变化而变化,利用土壤测试方法得到的锰素营养丰缺指标,通常难以代表田间锰素营养的实际状况.然而,在应用土壤pH和氧化锰溶解度的关系时,某些文献的不确切解释,引起一些误解.本实验研究了在浓HCl、HNO3和H2SO4及其稀溶液的不同浓度情况下对二氧化锰-水钠锰矿(MnO2)的溶解能力和机理,以及三种卤素还原剂(KCl、KBr和KI)在两种pH值条件下对MnO2的还原能力,从实验上和理论上进一步阐明了pH和Eh对MnO2溶解度的影响.实验结果表明,在浓HCl中,MnO2能被Cl-迅速还原而溶解.而在浓HNO3和H2SO4溶液中,MnO2不能被酸所直接溶解,只能被酸中的H2O缓慢还原,放置两年后反应仍未到达终点.在稀酸溶液中,当H+强度小于0.5 mol L-1(pH＞1.0)时,三种强酸对MnO2都无明显的溶解能力;当H+强度＞1.0 mol L-1时,HCl对MnO2的溶解能力显著地高于HNO3和H2SO4.三种卤盐溶液对MnO2的还原能力为KI＞KBr＞KCl,并随pH的降低和浓度的升高而增强.当pH＞3时,KCl对MnO2的还原能力极弱;而无论pH高低(pH3或pH5),KI在很低浓度(0.001 mol L-1)时都能有效地还原MnO2.上述结果说明,如果二氧化锰不被还原,仅改变pH则很难被溶解.然而,在较高pH条件下,如有强还原剂存在,也有相当量的MnO2被还原.低Eh和pH条件下最有利于MnO2的还原.     

云南省典型县域烟田土壤肥力演变及综合评价

对云南省典型县域宾川县烟田土壤pH和养分含量40年的变化进行定量分析,明确烟田土壤肥力演变特征,进一步为烟区土壤养分管理及平衡施肥提供科学依据。通过数据收集和野外采样,分析宾川县1982、2012、2018、2022年4个时期烟田耕层土壤养分变化,运用土壤综合评价法,克里格插值定量评价了土壤综合肥力指数（IFI）及其时空变异特征。近40年来（1982—2022）,宾川县烟田土壤pH（7.13~6.23）和有机质含量（35.30~27.71 g/kg）呈下降趋势,有效磷（12.11~50.71 mg/kg）和速效钾含量（158.66~321.03 mg/kg）呈上升趋势,碱解氮含量（119.03~117.00 mg/kg）无显著变化。IFI（0.49~0.62）呈上升趋势,均值由1982年的0.49（Ⅲ）增加至2022年的0.62（Ⅱ）,其中平川镇、拉乌彝族乡、州城镇及宾居镇IFI增加幅度最大,当前高肥力区域主要分布于县东北部和南部,低肥力区域分布于西北部。此外,主成分分析表明影响烟田土壤肥力的主要内在因素由有机质变为速效钾。经过40年耕种管理,宾川县烟田肥力自西向东、自北向南逐渐增加,但养分指标非均衡性和肥力空间不均匀性增加,应稳定氮肥钾肥,减少磷肥施用。     

Crop management effects on soil carbon sequestration on selected farmers’ fields in northeastern Ohio

Soil organic carbon (SOC) pool is the largest among terrestrial pools. The restoration of SOC pool in arable lands represents a potential sink for atmospheric CO₂. Restorative management of SOC includes using organic manures, adopting legume-based crop rotations, and converting plow till to a conservation till system. A field study was conducted to analyze soil properties on two farms located in Geauga and Stark Counties in northeastern Ohio, USA. Soil bulk density decreased with increase in SOC pool for a wide range of management systems. In comparison with wooded control, agricultural fields had a lower SOC pool in the 0–30 cm depth. In Geauga County, the SOC pool decreased by 34% in alfalfa (Medicago sativa L.) grown in a complex rotation with manuring and 51% in unmanured continuous corn (Zea mays L.). In Stark County, the SOC pool decreased by 32% in a field systematically amended with poultry manure and 40% in the field receiving only chemical fertilizers. In comparison with continuous corn, the rate of SOC sequestration in Geauga County was 379 kg C ha⁻¹ year⁻¹ in no-till corn (2 years) previously in hay (12 years), 760 kg C ha⁻¹ year⁻¹ in a complex crop rotation receiving manure and chemical fertilizers, and 355 kg C ha⁻¹ year⁻¹ without manuring. The rate of SOC sequestration was 392 kg C ha⁻¹ year⁻¹ on manured field in Stark County.     

自控变频调速式灌溉水注肥装置的研究

为现代农业节水灌溉与精准施肥所需的配套注肥装置的开发,研究采用输液泵将肥料原液和酸碱调节液强行注入灌溉管网,并与灌溉水按比例混合获得一定浓度和酸碱度(EC & pH)的灌溉液。灌溉液浓度和酸碱度通过EC传感器和pH传感器检测并反馈PLC控制系统,通过变频调速进行EC值与pH值动态调节,实现节水灌溉系统的精准施肥灌溉。采用自控变频调速技术的灌溉水注肥装置经过实际运行,完全满足设计要求,可实现灌溉液的正常输送和EC值与pH的动态调节。特别是射流自吸泵变频调速技术的实现,不仅有效实现了灌溉液浓度（EC值）的动态调节,同时降低了设备成本,完全可用于节水灌溉注肥装置的开发。     

土壤初始含水率对优先流的影响简

土壤中优先流的存在会造成肥料利用率降低以及土壤深层甚至地下水污染.为确定土壤初始含水率对优先流的影响,通过室内含大孔隙土柱定水头入渗实验,以长武黑垆土及渭河砂土为研究对象,分析不同土壤初始含水率对优先流的影响.结果表明：1）相同质地,当土壤初始含水率大于其斥水性的峰值含水率时,湿润锋运移深度随着土壤初始含水率的增大而增大,反之湿润锋运移深度随着初始含水率的增加而减少,不同质地土壤湿润锋运移速度随土壤粉粒质量分数升高而减慢;2）累积入渗量受到土壤储水性及斥水性的双重影响,导致与湿润锋的运移趋势并不一致,黑垆土对照CK组及优先流O-C-30组（除7.04％含水率外）累积入渗量随着土壤初始含水率的增大而减小,渭河砂土CK组及O-C-30组均呈现2阶段特征,累积入渗量先随着土壤初始含水率的增加而减少,之后随土壤初始含水率的增加而增加;3）Kostiakov入渗模型能很好地拟合累积入渗量随时间的变化过程,适用于存在优先流的土壤入渗模拟.该研究结果对土壤优先流水分模拟具有一定的指导意义.     

Evidence of dissolved trivalent manganese in acidic forest soils

Background

Evidence of trivalent manganese (Mn³⁺) in the aqueous phase of soils is unknown so far although this strong oxidant has large environmental implications.

Aims

We aimed to modify a spectrophotometric protocol (porphyrin method) and to discriminate between Mn²⁺ and Mn³⁺ in the aqueous phase of forest soils based on kinetic modeling.

Methods

We investigated manganese speciation in 12 forest floor solutions and 41 soil solutions from an acidic forest site by adjusting pH and correcting for absorbance.

Results

The solutions showed broad ranges in pH (3.4−6.3), dissolved organic carbon (DOC, 1.78−77.1 mg C L⁻¹), and total Mn (Mn_T, 23.9−908 µg L⁻¹). For acidic solutions, a pH-buffer was added to increase the pH of the solutions to 7.5−8.0, and background absorption was corrected for colored solutions, that is, solutions high in DOC. This was done to accelerate the reaction kinetics and avoid overestimation of Mn_T concentrations. After the pH and color adjustments, the comparison of Mn_T concentrations between the porphyrin method and optical emission spectrometry showed good agreement. Trivalent Mn, which is stabilized by organic ligands, constitutes significant proportions in both forest floor solutions (10−87%) and soil solutions (0.5−74%).

Conclusions

The dissolved Mn³⁺ is present in acidic forest soils. Thus, we revise the paradigm that this species is not stable and encourage to apply the revised method to other soils.     

Co-amelioration of red soil acidity and fertility with pig manure rather than liming

Lime (calcium oxide), animal manure and crop straw soil treatments have been shown to ameliorate soil acidity, yet their effectiveness at concurrently enhancing soil fertility status and improving crop yields is less well understood. In this study, an acidic nutrient deficient red soil (Ferralic Cambisol) received these treatments at various dosage rates (% of DW soil) in pot experiments with maize plants. Lime was applied at four dosage rates (0.05%, 0.10%, 0.15% and 0.20%), pig manure at three rates (0.50%, 1.00% and 1.50%), maize straw or milk vetch at two rates (0.50% and 1.00%) and combinations of lime (0.10% or 0.15%) with maize straw (0.50%) and/or pig manure (0.50%). Soils treated with and without chemical fertilizers were also included as controls. Measurements of soil pH, exchangeable acidity, plant available nutrients and maize shoot biomass were recorded. Maize shoot biomass increased by 4.7–7.6 times under pig manure treatments, 1.1–1.6 times under milk vetch, 0.4–1.5 times under lime and 1.1–6.2 times under combination treatments, compared with the control. Soil pH increased by 0.5–0.9 units under lime, by 0.2–0.4 units under pig manure and by 0.7 pH units under the combination treatment relative to the control. Variance partitioning analysis showed that on an individual basis, soil acidity amelioration (pH, exchangeable H⁺ and Al³⁺) or nutrient input (C, N, P, K, Ca, Mg, Zn) explained only 4.3% and 5.6% of improved maize growth, respectively. Whereas, their interaction explained 85.9% of the variation. We also report that the over-application of pig manure could lead to P saturation and negative impacts on aquatic systems in the wider environment. Therefore, we recommend a combination of lime, pig manure and straw provides an optimal solution for addressing soil acidity and limiting P saturation in acid soils.     

Effect of calcareous and siliceous amendments on N2O emissions of a grassland soil

Liming of acidic agricultural soils has been proposed as a strategy to mitigate nitrous oxide (N₂O) emissions, as increased soil pH reduces the N₂O/N₂ product ratio of denitrification. The capacity of different calcareous (calcite and dolomite) and siliceous minerals to increase soil pH and reduce N₂O emissions was assessed in a 2-year grassland field experiment. An associated pot experiment was conducted using homogenized field soils for controlling spatial soil variability. Nitrous oxide emissions were highly episodic with emission peaks in response to freezing–thawing and application of NPK fertilizer. Liming with dolomite caused a pH increase from 5.1 to 6.2 and reduced N₂O emissions by 30% and 60% after application of NPK fertilizer and freezing–thawing events, respectively. Over the course of the 2-year field trial, N₂O emissions were significantly lower in dolomite-limed than non-limed soil (p < .05), although this effect was variable over time. Unexpectedly, no significant reduction of N₂O emission was found in the calcite treatment, despite the largest pH increase in all tested minerals. We tentatively attribute this to increased N₂O production by overall increase in nitrogen turnover rates (both nitrification and denitrification) following rapid pH increase in the first year after liming. Siliceous materials showed little pH effect and had no significant effect on N₂O emissions probably because of their lower buffering capacity and lower cation content. In the pot experiment using soils taken from the field plots 3 years after liming and exposing them to natural freezing–thawing, both calcite (p < .01) and dolomite (p < .05) significantly reduced cumulative N₂O emission by 50% and 30%, respectively, relative to the non-limed control. These results demonstrate that the overall effect of liming is to reduce N₂O emission, although high lime doses may lead to a transiently enhanced emission.     

恒电荷土壤及可变电荷土壤与离子间相互作用的研究 I.共存离子对NO_3~-吸附的影响

研究了我国典型３种可变电荷土壤和４种恒电荷土壤在陪伴阳离子分别为Ｋ十、Ｎａ十、Ｃａ２＋时和１ｍｍｏｌＬ－１ＫＣ１、Ｋ２ＳＯ４支持电解质中ＮＯ３－的吸附。结果表明，ＮＯ３－吸附量随ｐＨ的增加而减小。在添加相同浓度ＮＯ３－时，３种可变电荷土壤对ＮＯ３－的吸附量顺序为Ｃａ（ＮＯ３）２＞ ＫＮＯ３＞ＮａＮＯ３＞ＫＮＯ３十ＫＣＩ＞ＫＮＯ３＋Ｋ２ＳＯ４；在初始ＮＯ３－浓度０．５－５ｍｍｏｌＬ－１的范围内，吸附量随浓度变化的关系符合Ｌａｎｇｍｕｉｒ等温吸附式．由此求出与ＮＯ３－吸附结合能有关的常数（Ｋ）在不同共存离子存在下数值较小且差异不大，因此认为不同陪伴阳离子和不同伴随阴离子对ＮＯ３－吸附的电性机理影响不大，只是改变了土壤表面的正电荷数量从而使吸附量发生变化。４种恒电荷土壤对ＮＯ３－的吸附量通常很小，其中在Ｃａ（ＮＯ３）２介质中较在其他介质中稍大，最大吸附量仅为１．５～ｍｍｏｌ ｋｇ－１左右，约为可变电荷土壤的１／１０，且在浓度较低时常观察到负吸附。     

初始pH值对鸡骨素酶解液Maillard反应产物的影响

以鸡骨素酶解液为原料,研究了不同初始p H值条件下,添加木糖、半胱氨酸及硫胺素制备的Maillard反应产物(MRPs,maillard reaction products)在热反应过程中的特性变化。研究表明,p H值差异引起各体系氨基酸和总糖初始含量及变化趋势差异,p H值5、7和9体系反应终点多肽含量分别为100.11、100.01、104.55 mg·m L-1;与其它2个体系相比,p H值9体系分子量为2.3、1.39k Da的峰消失,出现峰面积较大的2.95k Da峰和较小的1.04k Da峰,褐变程度为p H值7体系的1.7倍;随着p H值升高,不同体系的MRPs风味主成分存在一定差异,p H值7体系的有机硫化物电子鼻响应值约为其它两个体系的1.6倍,p H值9体系的氮氧化物响应值最大。不同初始p H值影响添加物的含量及状态,导致各体系Maillard反应历程不同,引起MRPs化学组分的差异。本研究为鸡骨素酶解液MRPs风味及功能组分生成机制的研究及鸡骨高值化衍生产品的开发提供一定理论参考。