珠江三角洲平原土壤磷剖面分布及形态特征研究

以珠江三角洲平原由三角洲沉积物、河流沉积物和滨海沉积物发育形成的水耕人为土(水稻土)为对象,研究了水田、果园、菜地3种利用方式下不同发生层土壤全磷(TP)、有机磷(Po)、有效磷(AP)、无机磷(Pi)组分的含量和剖面分布特征,并利用液相31P核磁共振(NMR)技术测定了耕层土壤中磷形态分布。结果表明,珠江三角洲平原农田土壤全磷、有机磷、有效磷和各形态无机磷含量随土层深度增加呈减小的趋势,耕层土壤中全磷、有效磷、Al-P和Fe-P明显富集;菜地和果园耕层土壤中全磷、有效磷、Al-P、Fe-P、Ca-P和O-P含量均高于水田。土壤磷素以无机磷形态为主,无机磷、有机磷占全磷比例平均值分别为71.3%和28.7%。土壤无机磷组分以O-P和Fe-P为主,Al-P最低。Al-P、Fe-P、Ca-P、O-P与全磷呈极显著或显著正相关,有效磷与Al-P、Fe-P、O-P、全磷呈极显著正相关;Fe-P和Al-P是土壤有效磷的主要贡献者。31P-NMR结果表明,耕层土壤磷形态均以正磷酸盐为主;土地利用方式影响土壤磷组分,菜地耕层土壤中磷形态包括正磷酸盐、磷酸单酯和焦磷酸盐,水田和果园包括正磷酸盐、磷酸单酯、磷酸二酯和焦磷酸盐;水田土壤中正磷酸盐所占比例最低,磷酸单酯和磷酸二酯所占比例最高;成土母质对水田耕层土壤各形态磷所占比例影响很小。     

近三十年农田土壤磷分子形态的研究进展

农田土壤磷的赋存形态决定迁移、转化及归趋过程,单单通过全磷或有效磷含量并不能全面、准确、长效地评估土壤磷的养分供应能力和生态环境风险,探索可持续的农田磷素管理措施迫切需要能够科学表征、准确认识土壤磷形态。随着分析测试技术发展,农田土壤磷形态领域经历了以传统连续提取法为主的分级组分研究,到目前基于先进光谱技术的分子形态研究的发展历程。液相磷-31核磁共振技术(P-NMR)、基于同步辐射的X射线吸收近边结构谱技术(P-XANES)是当今土壤磷分子形态表征的主流技术,分别促进土壤多种有机磷和无机磷(铁磷/钙磷/铝磷)分子形态的有效识别。借助Histcite软件进行引文网络分析,梳理了近三十年(1990—2019年)土壤磷分子形态研究发展历程中具有重大借鉴意义的关键性成果,基于此综述了该领域的发展脉络,归纳发现农田土壤磷分子形态研究最初主要借助P-NMR技术侧重有机磷分子形态表征,而后过渡至与同步辐射XANES以及X射线微探针技术相结合,实现了土壤磷分子形态的全面认识。最后,对多谱学技术联用推动土壤磷分子形态研究的发展趋势进行了展望。     

长期施磷对山原红壤磷库组成及有效性的影响

通过33年施肥试验研究了不同施磷处理对山原红壤中磷素形态转化及含量的影响。结果表明,长期施用磷肥增加了红壤中全磷和速效磷的含量;施磷处理下土壤表层无机磷、有机磷显著积累。不同施肥处理下土壤无机磷组分均以Fe-P为主,占总量的50%左右;相关分析表明无机磷组分中的Fe-P、Al-P与速效磷分别呈极显著正相关(r=0.908)、显著正相关(r=0.706),表明Fe-P、Al-P为山原红壤的有效磷源。对于土壤有机磷而言,所有施肥处理的土壤中稳性有机磷比例最高,其次为中等活性有机磷,再次为高稳性有机磷,活性有机磷最低,前二者占有机磷总量的90%左右。有机磷组分与速效磷的相关性分析结果表明,中等活性有机磷、中稳性有机磷分别与土壤速效磷呈极显著正相关(r=0.861)、显著正相关(r=0.840)。说明中等活性有机磷和中稳性有机磷是土壤速效磷的主要来源。增施磷肥尤其是氮、磷、钾肥与农家肥配施后,可促进其他形态有机磷向有利于作物吸收的中等活性有机磷、中稳性有机磷转变。     

不同林龄杉木林下套种阔叶树对土壤磷组分的影响

套种是杉木人工林经营的重要措施,磷是南方森林生态系统中主要限制性养分元素之一,但套种模式对土壤磷素的影响尚不明确。以亚热带杉木人工林表层(0-10 cm)土壤为对象,研究套种林(杉阔套种幼林、杉阔套种成熟林)和杉木幼林土壤理化性质和土壤各形态磷含量差异,分析套种对杉木人工林土壤磷含量的影响。结果表明:(1)不同套种林显著改变土壤总磷、土壤总无机磷、土壤总有机磷、土壤微生物生物量磷(MBP)和土壤酸性磷酸酶活性(APA),大小顺序均为杉阔套种成熟林>杉阔套种幼林>杉木幼林。(2)土壤各磷组分中活性磷含量较低,其中NaHCO3-Po在活性组分中占主导;土壤NaOH-Po是中等活性磷的主要组分,杉阔套种成熟林尤为显著;闭蓄态磷(Residual-P)在总磷含量中最高。(3)与杉木幼林相比,杉阔套种成熟林显著增加了树脂提取态磷(Resin-Pi)、碳酸氢钠提取态有机和无机磷(NaHCO3-Pi、NaHCO3-Po)、氢氧化钠提取态有机和无机磷(NaOH-Pi、NaOH-Po)、氢氧化钠残留提取态有机磷(NaOHu.s-Po)、盐酸提取态磷(HCl-Pi)和闭蓄态磷(Residual-P)含量;土壤总无机磷、NaHCO3-Po、HCl-Pi、NaHCO3-Pi、NaOHu.s-Pi和Residual-P对杉阔套种幼林的响应不敏感。(4)除含水率外不同林龄下杉阔套种林土壤磷形态与土壤理化性质(土壤总碳氮、土壤可溶性有机氮、土壤微生物生物量磷、酸性磷酸酶)呈正相关性(P<0.05)。冗余分析表明,土壤磷组分的变化主要受MBP调控,且MBP与有机磷组分(NaOHu.s-Po、NaOH-Po)和HCI-Pi呈显著正相关。总之,套种林的土壤磷素有效性高于杉木幼林,土壤养分状况更佳。     

基于31P NMR的自然成土过程中有机磷组分演变特征及影响因素研究进展

土壤有机磷(P_o)是土壤中重要的磷库,其形态、含量与生物有效性随成土过程而发生变化,进而影响土壤磷素供应、养分平衡及生态系统生产力。然而,与土壤无机磷(P_i)相比,以往的研究对P_o的重视不够,这主要是由于土壤中P_o的提取、分析和鉴定方法难于P_i。近年来,随着液相³¹P核磁共振(³¹P NMR)波谱技术在土壤学领域的应用,为定量分析土壤P_o组分及含量提供了新的技术手段,同时为更好地理解生态系统演化过程中不同形态P_o的转化特征奠定了基础。本文主要总结了土壤P_o的种类和性质,介绍了液相³¹P NMR分析土壤P_o的原理和方法,在此基础上综述了自然成土过程中不同形态P_o的转化特征及其影响因素,并指出了需进一步研究的方向和关键科学问题：包括量化成土过程中不同形态P_o转化速率、途径与环境阈值,阐明...     

不同温室蔬菜种植模式下土壤磷素形态分布与转化

采用蒋柏藩-顾益初无机磷分级浸提法,研究了15a长期有机、综合和常规种植3种温室蔬菜生产体系下石灰性土壤磷形态分布及转化特征。结果表明:种植模式及施肥年限对土壤有机磷含量和各形态无机磷含量均有显著影响,且交互作用显著。随着施肥时间延长,3种种植模式土壤有机磷含量与无机磷形态Ca_2-P、Ca_8-P、Fe-P含量不断升高,Al-P、O-P、Ca_(10)-P含量呈现不规则变动,差异较小;有机模式土壤有机磷含量与无机磷形态Ca_2-P、Ca_8-P、Fe-P含量均高于常规和综合模式,O-P、Ca_(10)-P含量略小于常规和综合模式。在各磷素占比中,中等活性磷源(Ca_8-P、Fe-P、Al-P)潜在磷源(O-P、Ca10-P)有效磷源(Ca_2-P)。表层土中有机磷占全磷的8%～23%,亚表层土中有机磷占全磷的6%～13%。有机模式促进了无机磷各形态之间、有机磷和无机磷形态之间的转化过程,0～20 cm土层的磷素转化比20～40 cm更活跃。     

施加粪肥对潮土有机磷形态转化的影响

施加粪肥是提高土壤肥力的重要措施,为了解粪肥磷在潮土中的化学行为,通过室内培养试验,采用NaOH-EDTA 浸提和 31P 核磁共振技术分析比较了鸡粪、牛粪及施肥后土壤中的磷形态及含量,并研究了施肥对潮土有效磷的影响。结果表明,粪肥磷主要以无机态形式存在,2 种粪肥的有机磷形态及含量有明显不同,肌醇六磷酸在鸡粪中的含量明显高于牛粪。粪肥施加到潮土后丰富了土壤有机磷的形态。随时间延长,潮土中各形态磷发生相互转化,以肌醇六磷酸为主的正磷酸单酯含量明显降低,核酸等正磷酸双酯显著升高。鸡粪处理的土壤有效磷含量逐渐升高,牛粪处理则表现出相反的趋势。施加粪肥后,土壤有效磷呈现不同的变化规律可能是无机磷在土壤中固定或沉淀,有机磷矿化和无机磷被微生物固持这三方面综合作用的结果。     

施肥对采煤塌陷区复垦土壤理化性质和磷分级的影响

以山西省晋城市采煤塌陷区复垦土壤为研究对象,连续3年定位施肥研究施用有机肥(M)、无机肥(NPK)、有机肥+无机肥(NPK+M)对土壤理化性状、土壤磷分级的影响。结果表明:试验结束后,不同施肥处理土壤的pH、容重、全氮、全磷含量差异均不显著;单施有机肥处理的有机质含量显著高于单施化肥处理;有机肥+无机肥处理土壤速效磷含量高于其余处理,但处理间差异不显著。有机肥+无机肥处理能够明显提高土壤无机磷组分Ca_8-P含量;不同施肥处理均显著提高了Fe-P,处理间差异不显著;各处理的O-P、Ca_(10)-P增幅不明显;对照处理的不同无机磷组分含量总体保持下降趋势,其中Ca_8-P、Fe-P降幅较为明显。有机肥处理对活性、中活性组分,有机肥+无机肥处理对活性、中稳性有机磷效果明显,无机肥对有机磷组分效果不显著。相关性分析表明,Ca_2-P、Ca_8-P、Al-P、Fe-P、中活性、中稳性有机磷与速效磷均呈显著正相关性,Ca_8-P、中活性有机磷与速效磷极显著相关。     

磷肥对中酸性土壤无机磷形态转化及其有效性的影响

用张守敬Ｓ．Ｃ．Ｊａｃｋｓｏｎ提出的无机磷分级体系和蒋柏藩等新近改进的石灰性土壤无机磷的分级方法，对棕红壤和黄棕壤无机磷分级进行了比较研究，并用石灰性土壤无机磷分级方法，研究了棕红壤和黄棕壤施用过磷酸钙和磷矿粉肥前后无机磷形态的转化及其有效性。     

不同农田管理措施对土壤有机磷影响的研究进展

综述了土壤有机磷种类、来源、含量、分布及影响因素.重点介绍了不同耕作方式、秸秆还田、施用无机磷肥及有机肥对土壤有机磷变化的影响.开垦、轮作有利于土壤有机磷下降;秸秆还田、施用有机肥提高土壤有机磷含量,但由于有机物性质不同,有机磷组分转化不同.施用无机磷肥后,有部分无机态磷转化为有机态.外源有机酸、磷酸酶有利于有效性低的有机磷组分向有效性高的组分转化.     

不同施肥条件下红壤旱地磷素形态及有效性分析

磷素是红壤地区农业生产的最重要的限制因素，因此红壤磷素形态与转化问题的研究，对红壤地区农业生产具有重要意义。用Hedley方法对不同施肥条件下红壤旱地土壤磷素形态进行了研究，结果表明：施磷肥能明显增加红壤各形态无机磷含量和大多数形态有机磷含量；红壤中，对植物最有效的树脂磷和碳酸氢钠磷含量很少，铁铝结合态磷和残留磷含量很多；对有效磷（Bray磷）贡献最大的磷素形态是碳酸氢钠无机磷、铁铝结合态无机磷和存在于土壤团聚体内表面的有机磷。这对于了解不同施肥条件对红壤旱地磷素有效性的影响、探索磷素消长规律、指导红壤旱地磷素管理等都有一定的理论和实践意义。     

Influence of conifers on the forms of phosphorus in selected New Zealand grassland soils

We examined the effects of conifers on the forms of P in low-fertility tussock grassland soils using ³¹P nuclear magnetic resonance (NMR) and soil P fractionation. Results from field and glasshouse experiments clearly demonstrated that conifers enhanced the mineralization of labile (and to a lesser extent more resistant) forms of soil organic P which, in turn, increased amounts of labile inorganic P in the soil. These findings have important implications for P availability and long-term sustainable management of grassland soils in New Zealand.     

Characterization of Soil Phosphorus in Differently Managed Clay Soil by Chemical Extraction Methods and 31P NMR Spectroscopy

Changes in land use alter the natural cycling of phosphorus (P) in soil. Understanding the chemical nature of these changes is important when developing sustainable management practices for cultivated soils. In this study, we evaluated the ability of commonly used laboratory methods to characterize land use–induced changes in various P pools. Also, the characteristics of soil P revealed by different methods are discussed. Soil samples were taken from three differently managed field plots of the same clay soil: uncultivated grassland and organic and conventional crop rotations. Soil P reserves were characterized using Chang and Jackson and Hedley sequential fractionation procedures and by sodium hydroxide (NaOH)–ethylenediaminetetraacetic acid (EDTA) extraction followed by ³¹P NMR spectroscopy. Both of the tested fractionation methods identified differences in the P pools and provided evidence regarding land use–induced changes. However, the ³¹P NMR analysis suggests that the quality of organic P in this soil was not affected by the change in land use.     

Soil phosphorus mobilization in different taxonomic orders

Changes in P fractions using Hedley's sequential fractionation of organic and inorganic soil P, were studied in soils covering a wide range of developmental stages and original materials. A greenhouse experiment was performed in order to make an exhaustive P uptake by Lolium perenne and to study soil phosphorus mobilization from different fractions. Samples were obtained at 30, 60 and 90 days from sowing, with two fertilization rates added as KH₂PO₄. The exhaustion produced by plants resulted in different patterns of mobilization according to soil characteristics. For control soils the contents of inorganic labile fraction (LIP) decreased at the end of the experience in Mollisol (31%), Vertisol (24%) and Andisol (17%). The mobilization of organic P was greater for Ultisol and Andisol (77 and 75% respectively) than for the other soils. Fertilization affected mainly inorganic P, with a significant increase in contents of LIP in Entisol (46%) and moderately resistant inorganic P (MRIP) in Andisol (15%). Inorganic P/organic P relationship tended to increase during the experiment, while labile P/moderately resistant P increased in Entisol and Mollisol.     

Characterization of phosphorus in sub-alpine forest and adjacent grassland soils by chemical extraction and phosphorus-31 nuclear magnetic resonance spectroscopy

We used chemical extraction methods and ³¹P-nuclear magnetic resonance (NMR) to investigate the effects of vegetation on the amount and structural composition of phosphorous (P) in the sub-alpine soils of central Taiwan. Chemical extraction methods were used to measure inorganic P (Pi) and organic P (Po) in main soil horizons. The soil P composition was assessed by ³¹P-NMR spectroscopy on alkaline EDTA–NaOH extracts. According to the results of chemical extractions, the forest soil had a higher amount of Pi than the grassland soil, which might be a result of the mineralization of Po. ³¹P-NMR spectra showed inorganic orthophosphate (up to 67%) and orthophosphate monoesters (up to 75%) as the major forms of P extracted in forest and grassland soils, respectively. Smaller proportions of orthophosphate diesters and trace amounts of phosphonates and pyrophosphate were found. With possible hydrolysis of P compounds during chemical extraction and slight systemic error in the processes of extraction with NMR, the results from NMR analysis are, in general, consistent with those of chemical extraction.     

Characteristics of phosphorus fractions in the soils derived from sedimentary and serpentinite rocks in lowland tropical rain forests,Borneo

ABSTRACT

Soil organic phosphorus (P) is an important P source for biota especially in P-limited forests. Organic P has various chemical formations which differ in bioavailability and these organic P can be degraded by phosphatase enzymes. Here, we report soil P fractions inferred from solution ³¹P-NMR spectroscopy and soil phosphatase activities of two tropical rain forests on contrasting parent materials; sedimentary and ultramafic igneous (serpentinite) rocks. Compared to the sedimentary soils　and previous studies, P fractions of the serpentinite soils have distinctly high proportions of pyrophosphate and scyllo-inositol hexakisphosphate (scyllo-IP₆). The accumulation of pyrophosphate and scyllo-IP₆ may be related to strong sorptive capacity of iron oxides present in the serpentinite soils, which implies a consequent low P availability in the serpentinite soils. Mean value of soil phosphatase activities was higher in the serpentinite soils than in the sedimentary soils, suggesting that biota in these serpentinite forests depend more on soil organic P as a P source.     

The phosphorus composition of contrasting soils in pastoral,native and forest management in Otago,New Zealand: Sequential extraction and 31P NMR

The distribution and form of P in soil is central to the sustainability of agricultural practice. This study used sequential fractionation and ³¹P nuclear magnetic resonance spectroscopy (³¹P NMR) of NaOH–EDTA extracts to examine the influence of pastoral, native (undisturbed) and forest land use on soil P forms in 5 contrasting soils ranging from a Regosol to a Rendzina in Otago, New Zealand. Climatic factors likely to influence soil P distribution were negated by careful site selection. Together with a decrease in soil organic C (31%), total P decreased in forested soils (mean=674 mg kg⁻¹) compared to native soils (mean=784 mg kg⁻¹). In contrast, the ratio of inorganic to organic P increased (10%) probably due to mineralization of organic P in forest soils, while for pasture soils, accumulation of P in inorganic forms due to P inputs via fertilisers and animal dung was to blame. Investigation of the organic P forms in NaOH–EDTA extracts of each land use by ³¹P NMR indicated that diesters were greatest in the native soil (4–12% of total P in spectra), and declined as a proportion of total P in pasture soils and more so in forest soils. This was reflected in a decline of the diester to monoester ratio. However, the ratio was generally greater in forest than pasture soils and attributed to the labile nature of diesters, mineralization of monoesters in forest soils, and an increase in monoesters in pasture soils from inositol phosphates in plant debris. This effect was pronounced in the Regosol due to sandy texture and the preferential accumulation of plant debris in coarse particle size fractions. Due to the depletion of soil P reserves, forest soils in the area should be followed by pasture and well managed fertiliser additions before replanting.     

Phosphorus forms as affected by abandoned anthills (Formica polyctena Förster) in forest soils: sequential extraction and liquid-state 31P-NMR spectroscopy

Ants are known to concentrate phosphorus (P) inside their nests via collection of food and litter. To elucidate the possible effects on long-term availability of soil P, five anthills abandoned by Red wood ant (Formica polyctena Förster) > 5—20 years ago were characterized for soil P forms in a temperate Danish deciduous forest. Sequentially extracted P fractions and liquid-state ³¹P nuclear magnetic resonance (NMR) spectra were obtained on surface samples (0—10 cm) from abandoned anthills and adjacent topsoil; in addition one representative soil profile in an abandoned anthill was investigated. The results show that different inorganic and all organic P fractions were enriched by a factor of 2.0—3.3 inside anthills relative to the surrounding soil. The soil underneath the abandoned anthill had higher P contents until 50-cm depth. Phosphorus composition was less affected by former anthill construction. Only the younger anthills revealed a preferential accumulation of labile organic P forms such as Na-HCO₃ extractable P or diester P. The accumulation of the stable and moderate labile P forms, however, persisted for ≥ 20 years after abandonment. We concluded that former ant activity enhanced long-term P availability of soil due to high local P inputs, whereas changes of the P form distribution lasted 5—10 years after nest abandonment.