上海市城区土壤磷酸盐吸附解吸动力学特征研究

研究结果表明,在强酸性降雨径流(pH2)冲刷下,城市土壤磷酸盐的解吸量明显增加;当pH2时,降雨径流酸性强度大小对城市土壤磷酸盐的解吸量影响不大。城市土壤对磷酸盐的等温吸附曲线符合修正的Langmuir方程。在自然条件下,即使在酸雨(pH4.5)的条件下,酸碱度效应对城市土壤磷酸盐吸附量的影响较小;随固液比增大,城市土壤磷酸盐以解吸为主的趋势越明显。这说明城市土壤吸持外源磷的能力弱,土壤胶体所吸附的磷容易被解吸进入土壤溶液,从而随着土壤溶液流动进入城市水环境,导致水体中磷浓度增高。     

长期施肥对白浆土磷吸附与解吸的影响

对白浆土在长期施肥条件下磷的吸附与解吸进行了研究。试验结果表明，供试白浆土磷的等温吸附曲线符合langmuir方程，在低磷浓度下其吸磷能力较强，随着磷浓度的增大，吸磷能力减弱。在不同施肥处理中，CK处理的最大吸附量（Xm）最大，OM处理最小，各处理吸附常数（K）值变化较小，均在0．2左右，而Xm变化较大；不同施肥处理总的解吸趋势是一致的，即解吸量随着浓度的增加而增加，而后逐步趋于平稳。施有机肥的处理土壤吸附磷能力降低，但解吸磷能力增强；长期不施肥土壤固磷能力增强。     

pH对土壤吸持磷酸根的影响及其原因

本文选择了浙江、江苏15个性质变化范围较大的土壤样品,研究在两种支持电解质、不同pH条件下对磷酸根的吸持反应。结果表明,加碱提高强酸性土壤的pH值,导致交换性铝的水解和羟基铝聚合物的生成,增加对磷的吸持。磷酸根同酸性土壤的反应,可促进交换性铝的水解,释放出H⁺,降低体系的pH。在CaCl₂介质中,当pH>6时,可能有磷酸钙类盐形成,使溶液中磷浓度显著降低。有机质对土壤吸持磷有重要影响。在低pH下有机质通过与Al³⁺形成络合物,阻碍溶液中A1³⁺的水解,并与磷酸根竞争羟基铝化合物表面的反应点位,从而降低酸性土壤对磷酸根的吸附量。     

动物粪液中可溶性磷在土壤中的吸附和迁移特性研究

农田土壤施用动物粪肥引入了大量的可溶性有机物、有机磷和无机磷,了解这些可溶性物质在土壤中的相对移动性及它们之间的相互作用有助于指导农田养分管理。本研究从粪液中分离获得含水溶性无机磷、有机磷和有机物（碳）的溶液,选择了具不同质地和有机质含量的4个土壤（含高量有机质的黄筋泥、含低量有机质的黄筋泥、淡涂泥和清水沙）,应用等温吸附和土柱模拟淋洗方法研究了可溶性有机碳、无机磷和有机磷共存条件下,粪液中可溶性有机态磷和无机态磷在土壤中的吸附和迁移特性。吸附试验表明,可溶性有机物（碳）的存在大大降低了土壤对有机态磷和无机态磷的吸附,表明施用液态有机肥比施用化肥具有更大的磷流失风险。供试土壤对无机态磷的吸附强度高于有机态磷,但对二者的吸附量大小为:黄筋泥>淡涂泥>清水沙;并与粘粒含量、氧化铁含量呈正相关。有机质较高的土壤对有机磷的吸附明显低于有机质低的土壤。淋洗试验表明,在供试土壤中,这3种可溶性物质在土壤中吸持(包括生物吸持)的顺序为:可溶性无机磷>可溶性有机碳>可溶性有机磷;有机态磷比无机态磷更易在土壤中迁移。     

富啡酸对石灰性潮土中磷吸附-解吸及其对锌次级吸附-解吸的影响

通过吸附和解吸试验,研究了富啡酸（Fulvic acid,FA）对石灰性潮土中磷吸附一解吸的影响,并进行了吸附富啡酸和磷后对锌次级吸附一解吸的影响。结果表明：同时吸附不同磷和富啡酸后,土壤对磷的吸附量随磷初始浓度的增加而增加,而随富啡酸吸附初始浓度的增加而降低;石灰性潮土磷等温吸附曲线用Langumir方程式描述时,土壤对磷的吸附反应常数K、最大吸附量Xm、最大缓冲容量KxXm均随富啡酸初始浓度的增加而降低;KNO_3、KOH、HCI对吸附磷的解吸量所占比例及磷的总解吸量均随富啡酸浓度的增加而增加。土壤对Zn^2＋的吸附率随磷和富啡酸吸附初始浓度的增加而降低;而其解吸率随磷和富啡酸吸附浓度的增加而增加,说明磷和富啡酸减少了土壤对Zn^2＋的吸附,且增加了其在土壤中的解吸量。所以,石灰性潮土中富啡酸提高了土壤中磷的有效性,而且磷和富啡酸提高石灰性土壤中锌的有效性。     

锆改性沸石活性覆盖控制重污染河道底泥氮磷释放研究

通过实验考察了锆改性沸石对水中磷酸盐和铵的吸附去除作用,并考察了锆改性沸石活性覆盖控制底泥溶解性磷酸盐和铵释放的效率。锆改性沸石对水中磷酸盐的吸附能力随pH值的增加而降低：当pH值由4增加到5时,锆改性沸石对水中铵的吸附能力增加;当pH值5-8时,对铵的吸附能力较高;当pH值由8增加到10时,对铵的吸附能力下降。锆改性沸石对水中磷酸盐和铵的吸附动力学满足准二级动力学模型,并且对磷酸盐和铵的吸附速率比较快。Langmuir和Freundlich等温吸附模型可以用于描述锆改性沸石对水中磷酸盐和铵的吸附平衡数据,根据Langmuir模型计算得到的锆改性沸石对水中磷酸盐和铵的最大吸附量分别为7．75mg·g-1和9．59mg·g-1（pH7和25℃）。锆改性沸石对水中磷酸盐和铵的去除率随锆改性沸石投加量的增加而增加,其吸附水中磷酸盐的主要机制是配位体交换,吸附水中铵的主要机制是阳离子交换。被锆改性沸石所吸附的磷酸盐大部分（82．5％）以较为稳定形态磷（NaOH—P）存在,低溶解氧条件下不容易重新被释放出来。吸附磷酸盐后锆改性沸石中水溶性磷（WSP）、易解吸磷（RDP）和NaHCO,可提取态磷（Olsen—P）含量非常低,藻类可利用磷（AAP）含量仅占总磷含量的29％左右。低溶解氧条件下,重污染河道底泥会释放出大量的溶解性磷酸盐和铵,锆改性沸石活性覆盖则不仅可以使上覆水中的溶解性磷酸盐浓度控制到很低的水平,而且可以明显降低铵由底泥向上覆水迁移的速率。上述实验结果表明,锆改性沸石适合作为一种活性覆盖材料用于控制底泥溶解性磷酸盐和铵的释放。     

长期轮作与施肥对农田土壤磷素形态和吸持特性的影响

通过对黄土旱塬地区长期定位施肥(26a)条件下的不同轮作系统的土壤磷素形态和吸持参数的测定,研究了轮作和施肥对土壤磷素吸持特性和磷素形态的影响,以及土壤磷素吸持参数与磷素形态之间的关系。结果表明,长期轮作与施肥都可以减低土壤磷素的最大吸附量（Qm）,相对于其它轮作和连作,在氮磷（NP）施肥下,小麦-玉米-豌豆轮作可以减低土壤的Qm,在氮磷有机肥（NPM）施肥下,小麦-玉米轮作可以减低土壤的Qm。在施肥相同的条件下,小麦-玉米轮作和小麦-豌豆轮作可以显著增加土壤中各形态无机磷的含量,长期轮作比连作可以增加土壤中的有效磷养分,尤其对Ca2-P的提高效果更为显著。相关分析表明,Qm和磷吸持指数（PSI）与全磷（T-P）、Olsen-P、CaCl2-P、Ca2-P、Ca8-P、Fe-P、Ca10-P和有机磷呈极显著负相关（p＜0.01）,与闭蓄态磷（O-P）呈显著负相关（p＜0.05）,与Al-P关系不显著。土壤有机质（SOM）与Qm、PSI和磷最大缓冲能力（MBC）之间存在极显著负相关关系,与磷吸持饱和度（DPSS）存在显著正相关。通径系数和逐步回归分析表明,在石灰性黑垆土土壤的无机磷形态中,Ca2-P对Olsen-P的贡献最大。     

磷酸盐吸附对可变电荷土壤正负电荷的影响

本文研究了华南地区不同类型的可变电荷土壤，并对磷酸盐的吸附量和吸附磷后土壤的正、负电荷的变化，以及ｐＨ和游离氧化铁对这种变化的影响进行了研究。结果表明，土壤吸磷量与土壤游离氧化铁含量成良好的正相关。土壤吸磷后正电荷减少，负电荷增加，土壤电荷量与吸磷量之间呈抛物线状相关。吸附１摩尔磷酸盐对土壤净负电荷的贡献在０．３－１．０摩尔之间。土壤中的游离氧化铁使吸附的磷对土壤负电荷的贡献减少。     

有机阴离子对磷酸根吸附的影响

在中性条件下,低浓度的柠檬酸、草酸、酒石酸和胡敏酸阴离子都能显著降低针铁矿、非晶氧化铝、高岭石和红壤对磷酸根的吸附,尤其在低磷吸附饱和度下效果更好。有机阴离子抑制磷酸根吸附的能力因有机酸的种类和性质、以及固相的表面特性而异。有机阴离子存在下吸附的磷酸根具有较高的同位素³²P交换活性和解吸率。测定了吸附平衡溶液中铁和铝的浓度。结果表明,在实验条件下(pH 7.0),即使较高浓度的有机酸根(10^-2mol)也只能溶解极少量的铁和铝。有机阴离子络溶作用不足以说明固相吸附磷能力的显著下降。可见,有机阴离子降低磷酸根吸附的机制主要是竞争专性吸附。有机阴离子占据了一部分高亲和力的吸附位,从而降低了土壤固相吸附磷的量,增加了吸附态磷的活性。     

不同年限稻田红壤发生层土壤磷的固持容量及其释放潜能研究

以江西鹰潭孙家典型红壤小流域中期稻田(MP)、新稻田(NP)与老稻田(OP)的发生层土壤为研究对象，基于吸附-解吸实验与结构方程模型，分析了稻田红壤各发生层土壤磷的固持能力(PSI)、最大固持容量(MCSP)及释放潜能的变化差异与影响因子，明确了固定态磷的释放机制与流失风险。结果表明：随发生层深度的增加，稻田红壤PSI及MCSP逐渐增大，二者变化分别为：MP > NP > OP与NP > MP > OP；但稻田红壤发生层中电性吸附态磷(CaCl2-P)及OP剖面专性吸附态磷(EDTA-P)逐渐降低，而MP剖面和NP剖面的EDTA-P以及稻田红壤发生层的残留态磷(Red-P)则相反；OP剖面发生层CaCl2-P与EDTA-P的比值随发生层深度的增加呈逐渐升高趋势，且显著高于MP和NP剖面。结构方程模型分析结果表明，土壤有机质、全磷、pH和铁铝氧化物之间相互作用且协同调控着稻田红壤的磷吸附位点数量及其吸附-解吸能力。稻田红壤水耕层(Ap层)土壤吸磷能力弱、释磷能力强，土壤磷流失风险大；而氧化还原层(Br)和母质层(C)土壤吸磷能力强、释磷能力弱，土壤磷固持容量大。与新稻田和中期稻田剖面相比，老稻田发生层土壤中吸附态磷更难以向专性吸附态磷及残留态磷转化，土壤磷流失风险相对较大，需及时采取相应的调控措施。     

Phosphate sorption by calcareous Vertisols and Inceptisols as evaluated from extended P-sorption curves

The plant availability of phosphate applied to calcareous soils is affected by precipitation and adsorption reactions, the relative significance of which is not well known. We used extended P-sorption curves obtained at phosphate addition rates up to 340 mmol P kg^?1 soil to examine the relative contribution of precipitation and adsorption by 24 calcareous Spanish Vertisols and Inceptisols. Adsorption was dominant at 1 day and at small rates of addition (10–35 mmol P kg^?1). With increasing clay and Fe and Al oxides contents of the soil, more phosphate was sorbed before the sorption curve bent upwards, as a result of Ca phosphate precipitation. Sorption curves showed a nearly vertical intermediate region, the length of which increased with time, suggesting that a Ca phosphate buffered the concentration of P in solution. The buffering concentration decreased with time, suggesting a progressive transformation of more to less soluble forms of Ca phosphate. A phase less soluble than octacalcium phosphate seemed to control the concentration of P in solution at 180 days in most soils. The apparent solubility of this phase decreased with increasing carbonate content in the soil. Precipitation of poorly soluble Ca phosphates apparently predominated up to a P addition dose ranging from about 30 mmol P kg^?1 in some soils to more than 340 mmol P kg^?1 in others. At larger doses, the way additional P was bound to the solid phase was different; phosphate was probably adsorbed, at least in part, to low-affinity sites on silicate clays and oxides. The proportion of sorbed phosphate that was isotopically exchangeable decreased with time, soil carbonate content and P addition dose for doses <100 mmol P kg^?1. This is consistent with the idea that P in Ca phosphates is less isotopically exchangeable than P adsorbed on mineral surfaces. At larger additions of P, isotopic exchangeability was unrelated to the soil properties measured, probably because there was a variety of sorbed P forms influenced in turn by different soil components.     

Assessing the fixation and availability of sorbed phosphate in soil using an isotopic exchange method

An isotopic exchange method was used to characterize quantitatively the fixation and plant availability of phosphate previously sorbed by soils. In general, the exchangeability of the sorbed phosphate was much higher than its desorbability for both soils and clay minerals. Isotopic exchangeability of the sorbed phosphate increased with sorption saturation during the initial stage (15–60% saturation), but the increase was less with increasing saturation from 60–90% for all soils tested. Therefore a sorption saturation of 60% was recommended as the upper limit of P fertilization in terms of economical efficiency. For clay minerals, with increasing sorption saturation, the isotopic exchangeability of the sorbed P increased significantly for kaolinite and sesquioxides, but decreased for montmorillonite. Most of the phosphate sorbed by montmorillonite and kaolinite was found to be isotopically exchangeable, but only a small amount of the P sorbed by goethite could be exchanged. The P sorbed by Al oxide exhibited isotopic exchangeability between that of kaolinite and Fe oxide. The isotopically exchangeable phosphate pool could readily account for the P uptake of plants and the available P determined by some commonly used chemical methods, such as Olsen-P and Bray-P.     

Phosphate sorption in some representative soils of Bangladesh

An experiment was conducted to observe the phosphate sorption potential of some soils of Bangladesh. Three soil series of calcareous origin, namely Sara (Aquic Eutrochrept), Gopalpur (Aquic Eutrochrept) and Ishurdi (Aeric Haplaquept), and two soil series of non-calcareous origin, namely Tejgaon (Rhodic Paleustult) and Ghatail (Aeric Haplaquept), were selected. The soils were equilibrated with dilute solution of calcium chloride containing graded concentrations of phosphate (0, 1, 2, 5, 10, 25 and 50?μg?P?mL^?1), and the amount of phosphate sorbed or desorbed was determined. Although all the soils showed potential for sorbing phosphate from applied phosphorus, their ability to sorb phosphorus differed. Increasing rates of phosphate application increased the amount of P sorption but reduced phosphate sorption percentage in all soils except Tejgaon. Phosphate was sorbed by the soils in the order: Tejgaon > Ghatail > Ishurdi > Gopalpur > Sara at 50?μg?P?mL^?1 application. Soils possessing higher amounts of free iron oxide and clay sorbed more phosphate from applied phosphorus.     

Transformation and bioavailability of specifically sorbed phosphate on variable-charge minerals in soils

Crop production on red soils in China is largely limited by the low availability of phosphorus, which is frequently attributed to the adsorption of phosphate by variable-charge minerals including Fe and Al oxides and kaolinite. Isotopic tracing analysis and soil incubation were carried out to investigate the desorption and microbial transformation of applied specifically sorbed P in two pH-contrasting light-textured soils. A rapid release of P from the added mineral-P surface complex in the two tested soils was observed. Most of the released P was recovered in a 0.5MNaHCO₃ extract and in soil microbial biomass. Microbial biomass-³²P was detected at early stages of incubation and reached up to 10–30% of the added ³²P. Approximately 50–70% of the added complex ³²P, varying between minerals and soils, was extractable in the 0.5MNaHCO₃ at 75 days after incubation for the acid soil but up to 120 days for the neutral soil. Microbial biomass-P plus 0.5MNaHCO₃-extractable ³²P accounted for more than 60–80% of total added complex-³²P, implying high desorption and transformation of the specifically sorbed P in the two soils. There was more inorganic ³²P than organic ³²P in the NaHCO₃ extract, suggesting that chemical release of specifically sorbed P was dominant. Ligand exchange and chemical desorption due to a change in environmental conditions such as pH and ionic strength are likely the major mechanisms responsible for the chemical release of specifically sorbed ³²P in the tested soils. Received: 29 September 1996     

DESORPTION AND ISOTOPIC EXCHANGE RELATIONSHIPS OF PHOSPHATE SORBED BY SOILS AND HYDROUS FERRIC OXIDE GEL

Sorption of added inorganic phosphate (P) was irreversible in four contrasting soils and hydrous ferric oxide gel during 16 h desorption after 40 h sorption at the same (iso)pH. Irreversibility increased with increasing time of desorption above 30 h. When the amount of P which was chemisorbed during the sorption step was subtracted from the amount desorbed, the latter fell on the isotherm describing the more-physical, potential-determining sorption. No pH change occurred during desorption and net negative charge decreased by 1 equivalent per mole P desorbed. These results suggested that only more-physically sorbed P was desorbed at the iso-pH. The more-physically sorbed P was also reversible with respect to changes in the ionic strength and cation species of the desorbing solution. The isotopic exchangeability of the more-physically sorbed P was at least ten times greater than that of chemisorbed P. With increasing sorption time, both the ease of desorption and exchangeability of sorbed P decreased. Subsequent to desorption, the exchangeability of the remaining sorbed P also decreased. These observations are interpreted in terms of the concurrent changes in the amounts of chemisorbed and more-physically sorbed P.     

Preferential Soil Sorption of Oxygen-18-Labeled Phosphate

Oxygen-18-labeled phosphate (OLP) and natural abundance ¹⁸O have been used as tools for elucidating the dynamics of phosphorus (P) in soils, yet much remains poorly understood. The objective of this research was to determine the extent of preferential soil sorption across the range of species contained within OLP. A variety of soils were shaken with water containing 65.5 mg L^?1 OLP-P for a 24-h period. Following shaking, the OLP species remaining in the solution were determined. Increasing the oxygen-18 atoms in the phosphate molecule by one resulted in a 1.8% increase in the amount of that OLP species sorbed to the soil, and this increase in sorption was uniform across soils. A strong correlation (r² = 0.94) was found between the amount of phosphate sorbed and the Mehlich 3 P saturation ratio of the soil. These results will be useful for studies using natural abundance and enriched ¹⁸O-phosphate in soils.     

Phosphorus fractions and dynamics as affected by land-use changes in the Central Mexican highlands

Land-use change from forest to agriculture in the volcanic ash-derived soils of Mexico has increased over recent decades. It is likely that land uses and management practices, particularly fertilizer use have affected phosphorus (P) distribution and availability. The objective of this study was to evaluate the effects of land-use types (native forest and maize mono-cropping), and the related P addition, on the forms and distribution of soil P and their isotopic exchangeability. An Andisol, sampled from a cropping site, along with the contiguous area under native forest was treated with ³²P-labelled potassium phosphate (KH₂³²PO₄). The soil samples were extracted after incubation times of 7, 21, 35 and 49 days. Phosphorus content and ³²P recovery in fractions sequentially extracted were assessed for each incubation time. Total soil P was dominated by inorganic fractions (79 to 86%) in both land-use types. Resin-Pi, bicarbonate extractable inorganic P (Bic-Pi) and sodium hydroxide extractable inorganic P (NaOH_0.1-Pi) were all raised with P addition. However, the proportion of organic P fraction was reduced under cropped soil. The recovery of ³²P in soils with P addition indicates that resin-Pi, Bic-Pi and NaOH_0.1-Pi comprised nearly all the exchangeable P. In native soils with no P addition, more than 19% of the ³²P was recovered in Bic-Po and NaOH_0.1-Po forms. This finding indicates that organic P cycling is crucial when soil Pi reserves are presented in an inadequate amount. Ecologically based management has to be designed for replenishment and succeeding maintenance of soil organic P compounds to increase sustainable agricultural production.     

Changes in distribution of inorganic soil phosphorus forms with phosphate desorption by iron oxide‐impregnated paper strips

Abstract

The release of soil phosphorus (P) to solution has been described by extraction of soil with iron (Fe)‐oxide coated paper strips. Little information is available, however, on where this P is coming from. The effect of removal of reversibly adsorbed soil P on the distribution of inorganic P forms was investigated for 12 Italian soils. Phosphate was removed from these soils by Fe‐oxide strips after incubation with P (0 and 100 mg P kg^‐1) for 90 days. With no applied P, 3 to 17% of the total soil active P [saloid‐P, aluminum‐phosphate (Al‐P), iron‐phosphate (Fe‐P), and calcium‐phosphate (Ca‐P) was removed by the Fe‐oxide strips. The change in strip‐P following P addition (100 mg kg^‐1 soil), ranged from 12.9 to 53.5 mg P kg^‐1, with P coming almost entirely from the active P fractions. A close relationship between the changes in desorbed strip‐P after P equilibration and soil P sorption index (SI) was found for the studied soils (r²=0.96). Thus, the release of soil P for plant uptake or transport in runoff was a function of the amount of “actively”; sorbed P and an estimate of P sorption.     

Testing a mechanistic model. XI. The effects of time and of level of application on isotopically exchangeable phosphate

A model for the reaction of ions with soil was improved to permit time trends to be followed at a given level of phosphate addition. Difference equations were also developed to describe the rate of reaction of ions with both vacant sites and occupied sites, while diffusive penetration of the surface was occurring. The model was applied to data for the effects of time and of level of application on exchangeable phosphate. Many of the observed values for isotopically exchangeable phosphate could be well-described if it was assumed that equilibration of ³²P with surface sites was very rapid and this was followed by a diffusive penetration into the adsorbing particles. However, for short periods of contact between soil and ³²P, it was necessary to also take into account the rate of the reaction between ³²P and surface sites. This reaction was largely with vacant sites. Reaction with occupied sites–that is, true exchange–was unimportant. It is suggested that the electric potential of the surface may determine whether reaction is with occupied or vacant sites. In contrast to reaction of ³²P with occupied sites, reaction with vacant sites involves a net transfer of charge. Reaction with vacant sites would be slow if the potential was large and negative. It is shown that when reaction with vacant sites is slow, the proportion of previously added ³¹P recorded as exchangeable increases with level of addition of ³¹P. This may explain published observations of slow and non-linear exchange in some soils.