不同分子量腐植酸的结构特征及其对土壤镉有效性的影响

为探究不同分子量腐植酸组分的结构特征,本研究利用褐煤粉提取腐植酸进行超滤分级,获得四个不同分子量的腐植酸组分。研究发现,分子量大于50 kDa和小于1 kDa的腐植酸分别占总腐植酸的49.66%、47.07%,中间两个组分占比很小；腐植酸的理化性质和功能主要是由1 kDa以下的腐植酸和50 kDa以上的腐植酸所决定的。1 kDa以下的腐植酸总酸性基、羧基和酚羟基官能团含量最高,酚羟基占总酸性基的比例也较高,腐植酸的芳香化程度、缩合度随分子量的增大而增大,含氧官能团含量、E4/E6值随分子量的增大而减少。通过盆栽试验,探索了不同分子量腐植酸对土壤镉有效性的影响,土壤对镉的吸附量随腐植酸分子量的增大而减少,各处理均在500 mg/L时达到吸附平衡；土壤镉的解吸量亦随腐植酸分子量的增大而减少。小分子量腐植酸的酸性官能团丰富,对土壤重金属的吸附络合能力更强,可以降低土壤对镉的吸持能力,提高其移动性和生物有效性；大分子腐植酸则主要起吸持和固定作用,降低重金属的移动性和生物有效性。     

Improvement of Iron Uptake in Table Grape by Addition of Humic Substances

Two experiments in consecutive years were conducted at a table grape plantation located in southeastern Spain. The objective was to test whether the addition of commercial organic compounds could improve the uptake of iron (Fe) by plants. A commercial humic substance and two mixtures of amino acids were used as organic compounds in the first experiment and FeEDDHA was the source of Fe. The joint addition of FeEDDHA and organic compounds improved Fe nutrition. The humic substance was more effective than the amino acids in increasing Fe uptake. In the following year, a similar experiment was conducted by progressively replacing part of the chelate with the humic substance. An increase in foliar Fe and phosphorus (P) and a decrease in sodium (Na) levels were observed. The best results with respect to nutrient foliar content and nutrient relationships were obtained for a range of substitutions for the chelate by the humic substance of from 30% to 50% with no loss in yield or fruit quality.     

不同来源腐殖酸的组成和性质的研究

本研究从三种有机物料草炭、褐煤、风化煤中提取腐殖酸,对其组成和性质进行了测定,同时对胡敏酸进行酒精沉淀分级。研究结果表明:褐煤胡敏酸氧化度和芳香度最高,其次为风化煤胡敏酸,最后是草炭胡敏酸;风化煤富里酸的氧化度和芳香度最高,其次为褐煤富里酸和草炭富里酸。胡敏酸各级分的回收率均随着级分数的升高而增加。回收率以风化煤胡敏酸最高,依次为褐煤胡敏酸、草炭胡敏酸。     

不同来源腐殖酸对铜吸附量和吸附机制的研究

本研究从三种供试材料:草炭、褐煤和风化煤中提取腐殖酸,采用NH4OAc和EDTA两种解吸剂,研究三种来源腐殖酸对Cu2+的吸附能力和吸附机制。研究结果表明:三种来源腐殖酸对Cu2+的吸附在吸附量上没有明显差异,但吸附机制却并不完全相同。三种来源腐殖酸对Cu2+的吸附均主要通过离子交换和络合(或螯合)作用,其中,草炭和褐煤提取的腐殖酸的离子交换作用显著大于风化煤提取的腐殖酸,而风化煤提取的腐殖酸的络合(或螯合)作用则明显大于草炭和褐煤提取的腐殖酸。     

腐殖酸对外源砷在土壤中形态转化和有效性的影响

通过室内培养的方法,探讨腐殖酸(HAs)的两种活性组分——富里酸(FA)和胡敏酸(HA)及其不同比例(HA/FA)对土壤As形态转化及有效性的影响。结果表明,HAs的两种组分对土壤As的形态均具有显著影响,其影响程度和方向与其浓度、比例及外源As含量有关。FA和添加量≤1%C的HA能增加土壤交换态As(Ex-As)的含量,添加量≥3%C的HA能降低土壤Ex-As含量;两种组分都能降低土壤铝型As(Al-As)和铁型As(Fe-As)含量,增加残渣态As(Res-As)含量,FA比HA的作用效果更强;在等量(1%C)HAs条件下,HA/FA≥5/5时HAs能降低Ex-As含量,≤3/7时则能增加Ex-As的含量。HAs对土壤有效As的影响是其对As形态分配综合作用的结果,对土壤有效As贡献最大的是Ex-As和Ca-As;HA和添加量较高(≥5%C)的FA能够降低外源As在土壤中的有效性,而添加量较低(≤3%C)的FA能在一定程度上增加土壤As的有效性。因此,掌握有机物料合理的用量和活性组分比例是其作为土壤As活性调控剂的前提。     

植物多酚与低分子量有机酸联合作用对紫色土铁形态分布的影响

植物多酚(PP)和低分子量有机酸(LMWOA)对土壤铁形态转化有重要影响。以酸性、中性和石灰性紫色土为研究对象,采用不完全随机区组试验,用2种PP(即表没食子儿茶素没食子酸酯(EGCG)和芦丁)和2种LMWOA(即柠檬酸和草酸)溶液浸提供试土壤,测定其可溶铁(Fes)、游离铁(Fed)、活性铁(Feo)、络合铁(Fep)含量,探讨了PP与LMWOA对紫色土铁形态分布的影响。结果表明:PP与LMWOA各自单独作用均能使酸性紫色土Fes增加、中性紫色土Fes减少;对于石灰性紫色土,PP会促进其Fes增加,而LMWOA作用相反。EGCG与LMWOA联合作用,在酸性和石灰性紫色土上均表现为LMWOA通过促使本应转化为Fes的转化为Fep而掩蔽EGCG对铁的溶解作用;芦丁与LMWOA联合作用,在酸性紫色土铁的溶解上表现为协同效应,在石灰性紫色土上则表现为LMWOA会抑制芦丁对铁的溶解作用;对于中性紫色土,PP与LMWOA联合作用可促进Fed向Fes转化而削弱PP对铁溶解的抑制作用。     

土壤胡敏酸的温和水解及分组研究 Ⅱ.胡敏酸水解产物中的醇类化合物

采用温和水解及薄层层析等分组方法 ,并应用气—质联机技术对土壤胡敏酸 (HA)水解产物中的醇类化合物进行了初步研究。结果表明 :HA水解产物中醇类含量顺序是饱和醇 >甾醇 >非饱和线性醇。饱和醇中主要是C12～ 3 0 中的偶数碳和C15,非饱和线性醇主要是C2 0 -1π、C2 0 -2π和C19-4π。C3 和C4植物条件下形成的HA有一定的差异 ,C3 -HA含有较多的非饱和醇 ,而C4-HA含有更多的饱和醇特别是C12 和C2 6。     

土壤腐殖酸对毒死蜱水解的影响

土壤腐殖酸的VIS-UV光谱特征和E465/E665的测定结果表明,各种土壤腐殖酸的VIS-UV吸收曲线相似,但吸收峰强度和E465/E665差异较大,进而推得它们的腐殖化程度排序为:紫色潮土腐殖酸>中性紫色土腐殖酸>酸性紫色土腐殖酸>腐殖土腐殖酸,说明它们在组成上有共同的本性,但结构和性质差异较大。在此基础上,研究它们对毒死蜱水解的影响。结果表明,不同来源土壤腐殖酸均促进了毒死蜱的水解,但它们的影响程度有明显的差异。对于腐殖化程度最低的腐殖土腐殖酸,浓度为120mg L-1时,对毒死蜱水解的促进作用最大,而随着腐殖酸浓度的增大,促进作用却越来越弱;而对于其它三种样品,腐殖酸溶液对毒死蜱水解的促进作用随着腐殖酸浓度增大而加强,其中以腐殖化程度较低的酸性紫色土的促进作用较为明显。可见,毒死蜱的水解速率与土壤腐殖酸的浓度和腐殖化程度有关。其中,腐殖酸腐殖化程度的影响机理主要与腐殖酸的酸性和腐殖酸的吸附—催化作用有关,其具体作用机理有待于进一步从定性和定量方面去研究,以更好地指导毒死蜱农药的合理施用和污染土壤的修复。     

红壤中腐殖酸对外源稀土形态的影响

本实验研究了腐殖酸 (HumicAcid ,又名胡敏酸 )对外源稀土元素在土壤中形态分布的影响和各形态的有效性。结果发现 ,加入腐殖酸后 ,土壤中稀土的交换态和碳酸盐结合态含量降低 ,有机结合态含量上升 ,而且腐殖酸浓度与稀土有机结合态含量有良好的相关性 ,说明腐殖酸能够提高稀土元素在土壤中的固定性 ,减少有效态稀土含量     

电荷辅助氢键对腐殖酸分子量和溶解性的影响

采用体积排阻色谱和总有机碳分析法,分别测定腐殖酸体系中加入盐酸、甲酸、乙酸和丙酸后其分子量和溶解性发生的变化;通过分析抗坏血酸、苯甲酸、苯酚和邻苯二酚4种模型化合物在甲酸影响下的紫外光谱,以验证电荷辅助氢键的存在。结果表明:小分子有机酸能够明显降低腐殖酸的分子量;此外,当腐殖酸体系pH接近小分子有机酸的pKa时(DpKa<0.5),腐殖酸溶解性明显增大。小分子有机酸可能与腐殖酸之间形成电荷辅助氢键,从而打破弱作用力维持的腐殖酸超分子的稳态结构,导致腐殖酸分子量的降低和溶解性的增加;且弱酸与有机物之间的pKa相差越小,形成的电荷辅助氢键能量越高,腐殖酸分子结构受到的扰动程度越大。一维紫外光谱和同步二维相关紫外光谱分析进一步表明,小分子有机酸可能与pKa接近的化合物之间形成电荷辅助氢键,整体跃迁所需能量提高,造成低波长吸收增大而高波长吸收减小的结果。     

几种胡敏酸和富里酸分子结构模型的三维可视化与特性研究

针对已提出的几种胡敏酸和富里酸的二维分子结构模型,应用HyperChem软件转换为三维结构并进行几何优化,计算了这些三维模型的能量以及定量构效关系(QSAR)参数。结果表明:几种模型在三维结构和特性上都各不相同,这为从空间角度更直观地认识腐殖物质的分子结构提供了可能性。     

Microbial Utilization and Transformation of Humic Acids Extracted from Different Soils

Humic acids (HA) extracted from Chernozem (Haplic Phaeozem), Brown Earth (Cambic Umbrisol) and Podzol (Humic Podzol) were added as a supplemental source of nutrients, or as the sole sources of carbon and nitrogen to aerobic cultures of complex microbial communities indigenous to the same individual soils. Depending on nutrient conditions in the individual cultures and origin of HA, between 14 and 86 % of the added HA was utilized. The formation of microbial biomass was enhanced up to six fold in the full-strength nutrient media supplemented with humic acids but was strongly inhibited if HA served as the sole C source. HA preparations re-isolated from the microbial cultures exhibited elemental and structural changes characteristic for early diagenetic transformations of humic substances. These included an increase in carbon content, C:N ratio, infra-red absorption typical for aromatics, and a decrease in infra-red absorption associated with aliphatic acids, nitrogenous and carbohydrate-like substances.     

土壤矿物和胡敏酸对阿特拉津的吸附-解吸作用研究

选取了6种土壤矿物(蒙脱石、高岭石、钙饱和处理蒙脱石、钙饱和处理高岭石、无定型氧化铁和无定型氧化铝),以及从土壤中提取纯化的3种胡敏酸为材料,采用批量吸附平衡法,研究土壤矿物和胡敏酸对阿特拉津的吸附特性。结果表明,各吸附剂对阿特拉津的吸附均能采用Frundlich方程进行较好地拟合(r≥0.982,p0.01)。胡敏酸对阿特拉津具有最大的吸附性能,其固-液分配系数(Kd值)随平衡浓度(Ce值)的变化基本恒定,吸附等温线呈线性(Frundlich方程常数N≈1),吸附以分配溶解作用为主,吸附可逆性较高。黏土矿物(特别是蒙脱石)对阿特拉津也具有较强的吸附能力,Kd值随Ce值增加而增加,吸附等温线呈S型(N1),吸附主要是通过表面亲水作用。无定型氧化铁铝的Kd值随Ce值增加而降低,当Ce达到一定水平后,Kd趋于恒定,吸附等温线呈L形(N1),吸附主要是通过无定型氧化物表面的羟基与阿特拉津分子间的化学键合作用,吸附可逆性最差。     

Humic acid effects on 2-hydroxypyridine metabolism by starving Arthrobacter crystallopoietes cells

Bacterial strains amended to soil to facilitate bioremediation of sites contaminated with organic substances must be capable of surviving and functioning in the presence of a variety of soil organic and mineral components. Thus, the influence of humic acid on 2-hydroxypyridine catabolism, retention of 2-hydroxypyridine catabolic activity by whole cells, and hydrophobicity of the Arthrobacter crystallopoietes cells was examined. Humic acid, added to the starvation medium of the arthrobacter cells, which had been acclimated to catabolize 2-hydroxypyridine, resulted in increased stability of this metabolic activity compared to that of comparable cells starved in the absence of humic acid. For example, after 7 days starvation, cells incubated in the presence of 0.1% (wt/vol) humic acid oxidized 2-hydroxypyridine at a rate of 54.9μmolh^–1 compared to 14.6μmolh^–1 in the absence of humic acid. Although after 1 day starvation 2.5-fold more 2-hydroxypyridine-catabolizing activity was detected in the presence of humic acid than in its absence, this enzymatic activity declined to undetectable levels after 3 days starvation both with and without humic acid in the starvation medium. No effect of humic acid was noted on protein content of the cells. Hydrophobicity of the cells was not affected by humic acid during the first 4 days of starvation but after 7 days humic acid lessened the reduction in this property. Thus, changes in cell protein content and hydrophobicity did not explain the effect of humic acid on 2-hydroxypyridine catabolism of starving A. crystallopoietes cells. Received: 21 March 1996     

Use of Humic Substances and Amino Acids to Enhance Iron Availability for Tomato Plants from Applications of the Chelate FeEDDHA

Two experiments in consecutive years were conducted in a commercial greenhouse located in the Southeast of Spain. The objective was to test if the addition of commercial organic compounds could improve the uptake of iron (Fe) by tomato plants (Lycopersicon esculentum mill.) cv Daniela. A commercial humic substance (HS) and a mix of amino acids (AA) were used as organic compounds in the first year of the experiment, and FeEDDHA (Q) as a source of iron. Both organic compounds improved iron uptake in comparison to a control without the addition of organic materials, especially the humic substance. A similar experiment was conducted the following year, but part of the chelate was progressively substituted by the humic compound. Results showed that the content of iron in the leaves increased with the substitution without any significant losses of yield or fruit quality. Plant nutrition was also improved because of an increase in the level of phosphorus in the leaves and a decrease in foliar sodium levels indicating a reduction in the effects of salinity.     

Investigation of Effects on Nutrient Uptake of Humic Acid Applications of Different Forms to Strawberry Plant

Abstract

The aim of this study was to investigate the effect of humic acid in liquid and solid form on uptake of nutrients for strawberry grown under greenhouse conditions. The experiment was designed in randomized block design with four replications for two years. Solid form of humic acid (Agrolig) that contained 85% humic acid was applied in the amounts of 0, 100, 200, 300, and 400 kg/ha before planting. Liquid form of humic acid (Blackjak) that contained 15% humic acid was applied by drip irrigation system at the concentrations of 0, 2500, 5000, 7500, and 10,000 mL/ha/month. Along with humic acid, 200 kg/ha nitrogen (N), 100 kg/ha phosphorus (P₂O₅), and 400 kg/ha potassium (K₂O) was applied by drip irrigation system after transplanting. According to the results, N, phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), iron (Fe), manganese (Mn), and copper (Cu) contents of the leaves were not affected significantly by the applications of solid and liquid humic acid forms. Applied liquid humic acid had a significant effect on the zinc (Zn) content of the leaves causing a decrease in the Zn content. Because of having excessive calcareous soil in the experimental area, uptake of nutrients in strawberry plants was not affected significantly. Applications of humic acid at high concentrations had an inhibitory effect on some of the nutrients.     

不同分子量碳源对砂姜黑土磷素有效性和玉米磷吸收的影响

为探究不同分子量碳源对土壤磷有效性的影响，以安徽省典型砂姜黑土为供试土壤，通过盆栽种植玉米试验，开展了不同碳源(果糖、蔗糖、纤维素)对土壤中磷形态转化和玉米磷吸收影响的研究。结果表明：(1)土壤Olsen-P含量随时间先增加后降低。在玉米间苗7 d后果糖处理Olsen-P含量最高，15 d后纤维素处理Olsen-P含量达最大值，90 d后，相比于对照、果糖和蔗糖处理，纤维素处理土壤Olsen-P含量显著增加了79.74%、54.03%和30.03%(P<0.05)。(2)玉米间苗90 d后，相较于对照处理，纤维素处理显著降低了Fe-P和Ca10-P含量，增加了Ca8-P含量，而对照、果糖和蔗糖处理的Ca2-P含量无显著差异。与对照处理相比较，纤维素处理显著提高了活性有机磷(LOP)和中等活性有机磷(MLOP)含量，减少了中稳定性有机磷(MROP)含量。(3)纤维素处理增加了土壤可溶性有机碳(DOC)含量和磷酸酶活性，降低了土壤p H和交换性钙含量，这是土壤磷有效性增加的重要原因；(4)与对照、果糖和蔗糖处理相比，纤维素处理下玉米磷吸收量显著增加了46.20%、19.05%和19....     

Lead Phytostabilization and Cationic Micronutrient Uptake by Maize as Influenced by Pb Levels and Application of Low Molecular Weight Organic Acids

ABSTRACT

Phytoremediation is a promising technique to clean up toxic heavy metals including lead (Pb). A greenhouse trial was conducted to evaluate the effectiveness of citric, succinic, malonic and oxalic acids on micronutrient uptake and phytoremediation of Pb contaminated soil by maize under different Pb levels. Mean root and shoot dry weights of maize decreased with increasing Pb levels. At the lowest Pb level, application of citric and oxalic acids caused increase effects on root and shoot dry weight, respectively, as compared to the absence of organic acid. As Pb levels increased, micronutrient uptake in maize shoot decreased. Among the studied organic acids, only the application of oxalic acid increased uptake of all micronutrients in maize shoot as compared to control at the lowest Pb level. Mean root and shoot Pb concentration and uptake and also uptake index noticeably increased at the highest Pb level. All tested acids increased Pb concentration and uptake in maize root. At the highest Pb level, organic acids, except for citric acid, significantly increased shoot Pb uptake and uptake index as compared to the absence of organic acid. Translocation factors less than 1, demonstrated that most of Pb taken up by maize accumulated in root as compared to shoot. According to results reported herein, application of malonic, succinic and oxalic acids is a good strategy to enhance phytostabilization potential of Pb by maize in pb-polluted soils.     

Humic Acids Derived from Leonardite-Affected Growth and Nutrient Uptake of Corn Seedlings

Using organic fertilizer or soil amendment such as humic substances is an important component for sustainable agriculture. The objective of this study was to determine the effects of different factions of humic acids (HAs) on corn seedling growth and nutrient uptake. The experiment was carried out with both an agar culture in root boxes and a hydroponic culture to which 400 mg/L of different factions of humus acids, mixed HAs, and raw Leonardite were added. The experiments were repeated twice with three replications for each treatment. The results showed that applications of HAs significantly improved the leaf and root growth of corn seedlings compared with the control (no HA addition). In the agar culture, seedlings treated with HAs with relatively low molecular weights had more leaves and twice long of roots compared to control and other treatments. In the hydroponic culture, the mixture of three factions was the best treatment for both shoot and root growth of seedlings.     

Influence of Iron Fertilization on Cadmium Uptake by Rice Seedlings Irrigated with Cadmium Solution

A pot experiment investigated the effects of iron (Fe) fertilization on cadmium (Cd) uptake by rice seedlings irrigated with Cd solution. Shoot dry weight was significantly affected by Fe addition, and root dry weight was affected by Cd addition. Iron supply was the dominant factor affecting the length of the longest leaf and the soil and plant analyzer development (SPAD) value. Cadmium concentrations were much greater in roots than in dithionite–citrate–bicarbonate (DCB) extracts or shoots, and a significant correlation was found between shoot Fe and Cd concentrations. Enhanced Cd uptake observed at high Fe supply implies that enhanced Fe nutrition may counteract the adverse effects of Cd on plants.