不同处理牛粪对植菜土壤腐殖质结构特征的影响

通过元素组成分析法、红外光谱分析法(IR)、核磁共振光谱分析法(13 C-NMR)等现代分析方法,研究施用新鲜牛粪、腐解牛粪和蛴螬牛粪2a后对植菜轮作土壤胡敏酸(HA)和富里酸(FA)的影响。结果表明,与单施化肥(CK)相比,不同牛粪处理对植菜土壤胡敏酸和富里酸的元素组成影响有较大的差异,各牛粪处理均引发植菜土壤胡敏酸C含量和C/H降低,O含量、O/C和(N+O)/C升高,富里酸C含量和C/N升高,N、O含量和O/C降低,降低了植菜土壤胡敏酸的缩合程度,升高了土壤胡敏酸的氧化程度和极性,降低了植菜土壤富里酸的氧化程度。不同牛粪处理使植菜土壤胡敏酸的脂肪族化合物减少,且均含有苯基碳、酚羟基C、芳香醚和(或)与O、N等取代基邻、对位的连H芳香C,使芳构化程度增加,富里酸的脂肪族化合物增加,芳香类、羧基类化合物减少,芳构化程度降低。不同牛粪处理的植菜土壤未改变土壤腐殖质的基本结构特征,只引起植菜土壤的结构单元和官能团数量上的差异。     

土壤中水溶性有机质的结构特征及其与富里酸、胡敏酸的比较

采用元素分析、1HNMR和FTIR研究了黄泥土中水溶性有机质组成及结构特征,并与富里酸、胡敏酸进行比较。结果表明:胡敏酸含有大量的芳香族不饱和物质,烷基链烃多,支链长;富里酸以含有大量的羧基为主要结构特征;水溶性有机质主要由碳水化合物组成,含有大量的羟基,芳香族不饱和物质少。     

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。     

秸秆还田条件下内陆盐碱土腐殖质的动态变化

采用室内培养试验的方法,研究了秸秆加入条件下内陆盐碱土的腐殖质及其组分(胡敏酸、富里酸)的动态变化。结果表明,在秸秆腐解过程中,盐碱土腐殖质、富里酸、胡敏酸含量均呈现持续上升趋势,分别平均增加了112.5%,269.54%和92.9%富里酸的含量明显高于胡敏酸的含量,是胡敏酸含量的约3~10倍。土壤的HA/FA(腐殖酸/富里酸)呈现出先增长后降低的趋势,并且在90d时达到平均最高值(0.283)。尿素添加量7.2g的处理土壤腐殖质含量在0.19%~0.38%,该处理秸秆分解的速率最快。土壤腐殖质和富里酸随着尿素含量梯度的增加呈现先上升,后下降,再上升的趋势,且分别平均增加了46.7%和55.3%胡敏酸的变化趋势与腐殖质相反,平均减少了14.3%HA/FA呈下降趋势,但下降趋势不明显。     

牛粪配施生物质炭的土壤碳净变化率和腐殖物质组成研究

牛粪是农业生产中常用的有机肥,牛粪配施生物质炭是否会提高有机物料在土壤中的碳净变化率是高效利用有机物料重要问题。通过1年田间试验施用常量(M1)和倍量(M2)牛粪、常量(CBM1)和倍量(CBM2)牛粪配施生物质炭对比了短期腐殖物质碳净变化率差异和结构特征。结果表明,与单施牛粪(M1和M2)相比,牛粪配施生物质炭(CBM2)土壤胡敏酸、富里酸和胡敏素的含量增至1.36g·kg~(–1)、2.50g·kg~(–1)和5.03g·kg~(–1);土壤胡敏酸和富里酸碳净变化率分别提高1.18%和3.67%。与施用牛粪相比,牛粪配施生物质炭胡敏酸、富里酸和胡敏素脂族碳和多糖相对含量增加;CBM2处理胡敏酸和胡敏素芳香碳相对含量增加,CBM1处理富里酸芳香碳相对含量增加。表明牛粪配施生物质炭在土壤固碳效果上优于单施牛粪,可形成更多的腐殖物质,提高胡敏酸和富里酸的碳净变化率;同时也有利于腐殖物质脂族碳和多糖相对含量的增加,而生物质炭用量不变的情况下,配施更多的牛粪可增加胡敏酸和胡敏素芳香碳相对含量。施用牛粪或牛粪配施低量生物质炭可使Hu和FA的缩合度增加,氧化度降低,而HA则相反。     

土壤腐殖质分组研究

采用Pallo法对两种耕地土壤腐殖质进行分组,初步研究了各组分的数量和结构特征。结果表明:焦磷酸钠提取的胡敏酸(HAp)是胡敏酸(HA)的主要组分;游离富里酸(FAf)是富里酸(FA)的主要组分;胡敏素(HM)的主要组分为非溶解性胡敏素(ISHM),而溶解性胡敏素(SHM)含量较低。通常随土层深度增加,HA、HM各组分的绝对数量和相对数量都下降;FA各组分的绝对数量也下降,而相对数量增加;HA/FA比值下降。一般来看,焦磷酸钠提取的富里酸(FAp)、氢氧化钠提取的富里酸(FAs)比相应的HAp、氢氧化钠提取的胡敏酸(HAs)的分子结构简单,铁结合胡敏素(HMi)比粘粒结合胡敏素(HMc)的分子结构简单;随土层深度增加,HAp、HAs的分子结构变简单,而HMi、HMc的分子结构变复杂。     

不同生物质材料对蕉园土壤有机质组成的影响

为探究不同生物质材料对蕉园土壤有机质及组成的影响,以木炭、椰壳炭、椰糠炭和与椰糠炭等碳量的椰糠为材料,分别以质量分数为2%和4%的用量加入土壤中,于室内常温培养并保持土壤含水量不变。在第15、30、60、90、120和180 d采集土壤,分析不同生物质材料对土壤有机质、胡敏酸、富里酸和土壤胡敏酸/富里酸的影响。结果表明:添加木炭、椰壳炭、椰糠炭和椰糠均能提高土壤有机质含量,并随添加量的增加而升高;添加木炭、椰壳炭、椰糠炭和椰糠均能加速土壤有机质的分解,添加椰壳炭对土壤有机质分解的影响相对较小。椰糠的添加主要是同时增加了土壤胡敏酸和富里酸碳含量,生物炭(木炭、椰壳炭和椰糠炭)的添加主要是影响了土壤胡敏酸与富里酸的相互转化。     

泥炭和褐煤对土壤有机碳和腐殖物质组成的影响

在相同温湿度环境条件下,研究泥炭和褐煤与土壤混合后对土壤有机碳及其腐殖物质组成变化的影响,为改善耕地土壤有机碳库的管理提供理论依据。结果表明:随着培养时间的延长,添加褐煤、木本泥炭的土壤有机碳含量分别上升了0.66%和17.41%,添加草本泥炭的土壤有机碳含量下降了3.15%;胡敏酸含碳量呈逐渐增加的趋势,富里酸含碳量呈逐渐减小的趋势;添加草本泥炭的胡敏素含碳量呈下降趋势,添加褐煤和木本泥炭的土壤胡敏素含碳量呈逐渐上升趋势。土壤胡富比和PQ值整体上都表现出随着培养时间的延长而逐渐增加的趋势。由此可知,泥炭和褐煤能提高土壤有机碳,改良土壤腐殖物质组分,且添加木本泥炭的土壤有机质含量和腐殖物质组分改善效果最好。     

生物炭对紫色土中腐植酸淋溶的影响

为了减少紫色土腐植酸的流失,提高龙川江流域紫色土肥力,采用土柱室内模拟方法,通过模拟降雨淋溶,研究了不同生物炭处理下(CK、1%、3%、5%和10%)对紫色土淋溶液p H值、电导率、体积以及胡敏酸和富里酸的影响。结果表明:在29 d试验过程中,淋溶液的p H值和电导率随着生物炭比例增加而增加;与CK相比,在1%、3%、5%和10%的生物炭处理条件下紫色土水分损失分别减少了6.33%、10.13%、16.46%和25.32%;胡敏酸浓度和累积淋失量随着生物炭比例增加而减小;除了1%和3%之外,富里酸浓度和累积淋失量也随着生物炭比例增加而减小;生物炭比例为10%的处理条件下对紫色土淋溶液中胡敏酸和富里酸浓度及累积淋失量最小,胡敏酸浓度和累积淋失量分别为1.46 mg/L、0.12 mg,富里酸浓度和累积淋失量分别为149.64 mg/L、29.60 mg,该处理有利于更大程度吸附胡敏酸和富里酸,减少其流失。     

热辐射对水稻土有机质组成的影响

本文研究了受不同程度热辐射后的水稻土中有机质组分的变化情况,结果表明:随温度升高,土壤中水溶性有机碳(DOC)含量先增加后减少,200℃变化尤为显著,增加为CK的3.68 ～ 7.45倍,中性糖、糖醛酸与DOC的变化趋势一致.辐射温度不同,土壤中的胡敏酸、富里酸组成和含量亦发生不同程度的变化,300℃胡/富比值最大(1.79 ～ 5.04),土壤腐殖质聚合程度增加;200℃胡敏酸的E4/E6比值最大,反映此温度下土壤芳香缩合度低、具有较多的脂族结构物质、土壤腐殖化程度低.     

The significance of solid‐state 13C NMR spectroscopy of whole soil in the characterization of humic matter

Abstract

Differences in characteristics of humic matter were investigated by solid‐state CP/MAS ¹³C NMR spectroscopy of whole (nontreated) materials and their extracted humic fractions. Samples used in the analysis were lignite, a commercial humate AG, and the Bh horizons of a Mascotte and a Lawnwood soil. Humic fractions were extracted by the 0.1 M NaOH or Na₄P₂O₇ (pH 9.8) method. The humic (HA) and fulvic acid (FA) obtained were weighed and analysed for total acidity, carboxyl and phenolic‐OH group contents. Whole lignite, humate AG and soil samples, and the HA and FA fractions were analyzed by solid state CP MAS ¹³C NMR and infrared spectroscopy. Carbon, H, and N contents were determined by chemical analysis. NMR spectra of the combined HA+FA extracts resembled the spectra of the whole materials. No additional signals were detected, indicating that alien compounds were not produced during the extraction. The best spectra were obtained with HA samples produced by the NaOH method. These spectra closely resembled those of the untreated materials. Spectral and chemical differences noticed between the HA (or FA) fractions were attributed more to differences in origin than to the extraction procedure. Aliphatic, aromatic and carboxyl groups were the major components of HA from lignite and humate AG. In contrast, HA from the two Haplaquods were characterized by four major components: the aliphatic, polysaccharide, aromatic, and carboxyl groups. Regardless of origin, all the HA fractions contained similar functional groups, as indicated by their close similarities in infrared spectra.     

溶液培养条件下腐殖酸对铁异化还原的影响

腐殖酸对土壤和水体环境中铁(Fe)的还原过程有重要影响。本文采用从山西大同风化煤、河南巩县褐煤、云南昆明滇池底泥中提取制备的腐殖酸,通过布置培育试验并接种土壤悬液,研究了不同来源的腐殖酸对无定形氧化铁异化还原的影响。结果表明:单独添加腐殖酸对氧化铁的还原几乎没有影响;而当同时添加腐殖酸与葡萄糖时,培养基质中氧化铁的还原过程显著加强;腐殖酸浓度越高对氧化铁还原的促进作用越明显。不同来源的腐殖酸因其复杂程度和结构不同,对氧化铁还原的促进作用有明显差异,其中山西大同风化煤提取的腐殖酸促进作用最大,云南昆明滇池底泥和河南巩县褐煤提取的腐殖酸之间则无显著差异。     

Nitric Acid Oxidation for Improvement of a Chinese Lignite as Soil Conditioner

Oxidation is known commonly to enhance humic acid (HAs) contents of coal, but in China, most humic substances are used directly as soil conditioners or applied in combination with fertilizers without oxidation. Therefore, we investigated the impact of nitric acid (HNO₃) oxidation on the characteristics of HAs derived from a Chinese lignite. The results showed that total HA content was increased by HNO₃ oxidation, thus consequently increasing its cation exchange capacity and moderate humification. Besides, HAs extracted from oxidized lignite were richer in oxygen-containing functional groups with smaller molecular size than natural lignite. Compared with natural lignite, retention capacities of nitrogen and potassium by oxidized lignite were significantly greater. However, phosphorus-retention capacity was decreased to near zero, which might enhance the availability of phosphorus in soil. In general, optimum HNO₃ oxidation had favorable effects on lignite and improved its characteristics for use as a soil conditioner.     

施用猪粪对棕壤胡敏酸和富里酸热力学参数的影响

应用Vodyanitsky提出的方法，根据元素组成数据，计算了施用猪粪对棕壤胡敏酸(HA)、富里酸(FA)热力学参数的影响。结果表明，HA、FA的形成都是自发进行的放热反应；与HA相比，FA的能态较低，分子结构有序度和热稳定性较高；FA在土壤中比HA更容易形成。施用猪粪后，HA、FA的能态降低，分子结构有序度和热稳定性也降低，形成的自发性减弱且放热量减少，这些与它们元素组成的变化有关。     

长施马粪对暗棕壤团聚体腐殖质数量和质量的影响

运用元素和红外光谱分析研究了暗棕壤长期施用马粪(每3年施肥1次)、施低量化肥和马粪配施高量化肥对水稳性大团聚体(2 mm和2~0.25 mm)、微团聚体(0.25~0.053 mm)和粉/黏粒粒级(0.053 mm)中腐殖物质-胡敏酸(HA)的分布及其结构特征的影响,探讨施肥对农田土壤肥力的贡献及其团聚体的固碳机制。施用马粪和马粪配施高量化肥分别提高(49.06%)和降低(31.04%)了2~0.25 mm大团聚体比例,3种施肥措施均提高了土壤有机碳(SOC)数量,但对土壤HA数量影响不显著。不同施肥措施对不同粒级团聚体中HA的分子结构特征影响不同,3种施肥措施均降低了2~0.25 mm大团聚体HA的缩合度,芳香性增加;微团聚体HA缩合度降低,脂族性增强;施用马粪提高了粉/黏粒HA的缩合度和脂族性,马粪配施高量化肥提高了粉/黏粒HA的缩合度和芳香性,施用低量化肥,粉/黏粒HA缩合度下降,芳香性提高。因此,长施马粪提高了土壤SOC数量,促进2~0.25 mm大团聚体的形成,大团聚体中HA的稳定性提高,利于土壤固碳,而0.25~0.053 mm微团聚体和0.053 mm粉/黏粒HA的活性增强,利于土壤肥力供给,这些团聚体是评估长施马粪对腐殖质质量产生影响的重要粒级。     

Characterization of water soluble organic matter in soils by size exclusion chromatography and fractionation with polyvinylpyrrolidone

Water extracts were obtained from four types of soils (Brown Lowland soil, Yellow soil with manure application for 6 years, non-allophanic Andosol, and allophanic Andosol), and the organic matter in the water extracts was fractionated according to the solubility in acid and adsorption onto polyvinylpyrrolidone (PVP). For the water extracts and their fractions, the amounts of organic C, total N, and anthrone-reactive C (ARC) were analyzed, and high performance size exclusion chromatography (HPSEC) was carried out. The PVP-non-adsorbed fulvic acid (FA) fraction accounted for the largest proportion of the total water-soluble organic C, ranging from 52% for the Yellow soil to 96% for the allophanic Amdosol, followed by the PVP-adsorbed FA and humic acid (HA) fractions. The water extract of the allophanic Andosol was characterized by the lack of HA fraction and a small proportion of PVP-adsorbed FA fraction. For all the water extract samples, more than 90% of the ARC was recovered in the PVP-non-adsorbed FA fraction. The proportion of ARC in the total organic C in the fraction was also highest in the PVP-non-adsorbed FA fraction. The molecular weight (MW) of the humic substances (HS) at peak maximum was estimated at 1,300 Da for the water extracts and their fractions from the Brown Lowland soil and non-allophanic Andosol samples by HPSEC using polyethylene glycols as MW standards. Manure application increased the MW of HS in the HA and PVP-adsorbed FA fractions. On the other hand, only a small amount of HS was found in the water extract of the allophanic Andosol by HPSEC.     

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。     

Effect of humic amendments on inorganic N, dehydrogenase and alkaline phosphatase activities of a Mediterranean soil

Dehydrogenase activity, alkaline phosphatase activity and NH₄ ⁺, NO₂ ⁻ and NO₃ ⁻ concentrations were monitored in an aridisol treated with three commercially available humic amendments. The materials were of plant residue, lignite and peat origins. The humus plant residues, fulvic acids, with a high content of Kjeldahl-N, sustained high enzyme activities and highest levels of NH₄ ⁺, NO₂ ⁻ and NO₃ ⁻. Humus lignite (mainly humic acids) produced the highest dehydrogenase activity, whereas the alkaline phosphatase activity was not as high as that amendment with humus plant residues. The lower activity of alkaline phosphatase could not be attributed to the higher P content of humus lignite. Nitrification was also low, probably due to the low N content of this fertilizer. The amendment of humus peat origin (only humic acids) did not increase enzyme activity or inorganic N concentrations of soil. Our results show that although these materials are widely utilized and recommended as microbial and plant activators, they all behave very differently, and the effects on soil microbiological activity cannot be predicted solely on the basis of their humic and/or fulvic acid contents.