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。     

不同供磷水平下澳洲坚果幼苗排根发生及其磷素利用

水培试验测试了澳洲坚果幼苗在6个供磷水平下排根的产生及对磷素利用情况, 结果表明: 随供磷量的升高(0.2~3.2 mol·L^-1), 澳洲坚果幼苗排根产生量、植株干重和排根占根系干重的比例均呈下降趋势; 供磷量由0.2 mol·L^-1升至1.6 mol·L^-1, 非排根酸性磷酸酶活性呈升高趋势, 排根酸性磷酸酶活性变化与非排根相反, 排根酸性磷酸酶活性平均比非排根高72.86%; 全磷含量为叶片>根系>茎, 0.2 mol·L^-1处理的澳洲坚果幼苗根系、茎秆和叶片全磷含量均高于其他处理; 与不施磷相比, 一定供磷量(0.2~0.4 mol·L^-1)可降低非排根酸性磷酸酶活性, 提高排根产生量、植株干重、排根占根系干重的比例和排根酸性磷酸酶活性, 进而增加澳洲坚果幼苗根系、茎秆和叶片全磷含量, 最终提高植株磷含量。在0~1.6 mol·L^-1供磷量下, 澳洲坚果幼苗排根产生量与植株干重、排根占根系干重的比例及茎秆、根系、植株磷含量呈显著和极显著正相关, 与排根酸性磷酸酶活性、叶片全磷含量呈90%以上正相关。     

有机酸对铝氧化物吸附磷的影响

以存在不同配位阴离子 (硫酸根、磷酸根、草酸根、柠檬酸根 )时合成的铝氧化物为对象 ,用平衡吸附法研究了草酸、柠檬酸等的浓度和 pH对铝氧化物吸附磷的影响 ,并讨论有机酸影响磷吸附的机制。结果表明 :六种合成铝氧化物的最大吸磷量 (Xm)介于 0.189～ 0.838mmol/g ,以Al(OH)x的吸磷量最高 ,铝 柠檬酸复合物 (Al-CA)的吸磷量最低 ;有机酸浓度升高时 ,铝氧化物的吸磷量降低 ,且柠檬酸的影响程度高于草酸 ;先加 pH为 2的草酸或酒石酸 ,Al(OH)x对磷的次级吸附量最低 ,而有机酸pH为 3时 ,Al(OH)x对磷的次级吸附量达最高 ,有机酸溶液 pH由 4增至 9,铝氧化物吸磷量变化不大或逐渐降低。有机酸与磷混合加入同单加磷相比 ,pH 3时差异较小 ,pH 4～ 6时差异最显著 ,pH 7～ 8时又减小 ;有机酸降低铝氧化物吸磷量的机理包括酸性溶解和络合竞争两方面 ,在 pH 2时以前者为主 ,pH 3～ 9时以后者为主 ,且铝氧化物表面的吸附点位对供试配位阴离子都是亲合的     

不同来源有机物料对菜用蚕豆生长和品质及根际土壤性状的影响

通过盆栽试验，分析了不同来源有机物料(鸡粪、牛粪、菇渣)对菜用蚕豆生长和品质、根际土化学和生物学性状的影响。结果表明：①3种有机物料对蚕豆分枝数、荚干重、籽粒干重、大粒重、大粒蚕豆占比、籽粒淀粉含量均有积极作用，其中牛粪和菇渣能显著(P<0.05)提高大粒蚕豆占比，鸡粪能显著(P<0.05)提高二粒荚和三粒荚的占比，并且对籽粒淀粉含量的提升效果最为明显(比对照增加69.1%)；②3种有机物料增加了根际土中细菌、真菌数量，显著(P<0.05)提高了根际土中性转化酶、脲酶、酸性磷酸酶、多酚氧化酶活性(除牛粪使中性转化酶活性提高不显著外)，其中鸡粪对细菌数量、中性转化酶活性、脲酶活性的提高程度均最大；③鸡粪能显著(P<0.05)增加根际土有机碳、全氮、NH₄⁺-N含量，牛粪、鸡粪能显著(P<0.05)提高土壤pH。大粒蚕豆占比与土壤酸性磷酸酶活性、有效磷含量呈显著正相关。蚕豆淀粉含量与细菌数量、中性转化酶活性、有机碳、全氮、NH₄⁺-N含量呈显著正相关，这说明有机物料的施用可能为细菌生长提供了更多的碳源和能源，导致细菌数量增加。细菌是酶的重要产生者，细菌数量的增加可能提高了碳氮循环相关酶(中性转化酶、脲酶)的产生量和活性，从而使更多的有机氮转变为无机氮(NH₄⁺-N)，提高了土壤养分(NH₄⁺-N、全氮)水平，进而提高了蚕豆营养品质。     

铁和不同形态氮素对玉米植株吸收矿质元素及其在体内分布的影响 Ⅱ.对铁、锰、铜、锌等营养元素的影响

用营养液培养方法研究了铁和两种形态氮素对玉米植株吸收铁、锰、铜、锌等微量元素及其在体内分布的影响。结果表明:与硝态氮(NO₃^--N)相比,铵态氮(NH₄⁺-N)显著提高了玉米对铁的吸收,降低了对锰、铜及锌的吸收。供铁也明显提高了植株地上部铁的吸收总量,降低了锰及锌的吸收量,尤其是在供应No₃^--N时这种作用更为明显。在缺铁条件下,NH₄⁺-N处理的玉米新叶中铁的含量明显高于NO₃^--N处理;而新叶、老叶、茎中锰、锌、铜含量以及根中锰、锌含量都明显低于NO₃^--N处理。但使用NH₄⁺-N时,根中铜的含量较高。在供铁条件下,NH₄⁺-N处理的玉米植株四个不同器官中锰和锌的含量显著低于NO₃^--N处理的植株,而铜的含量正好相反。在缺铁条件下,玉米新叶中活性锰、活性锌的含量显著高于供铁处理;与NO₃^--N相比,NH₄⁺-N的供应也显著降低了玉米新叶中活性锰以及活性锌的含量。     

电解质种类和浓度影响磷酸根解吸的机理研究

本文研究了吸附性阳离子、电解质浓度和组成影响几种矿物和土壤吸附态磷的解吸的机理。结果表明,吸附性阳离子影响磷酸根解吸与离子桥有关。桥接静电场愈强,被束缚磷的释放就愈困难。电解质阳离子对磷酸根解吸的影响则取决于其对表面负电荷的屏蔽效应。阳离子电价高,屏蔽作用大,磷解吸就少。电解质浓度影响吸附态磷的解吸主要与表面电位的变化有关。当pH>PZC值时,提高电解质浓度降低表面负电位,从而减少磷的吸附;当pH<PZC时,提高电解质浓度则降低表面正电位,促进磷的解吸。磷酸根解吸盐效应零点(P_PZSE)值一般都介于土壤或矿物样品吸附磷酸根前后测得的两个PZC值之间。不同浓度电解质溶液中磷解吸量之差与吸附层电位变化量(△ψ_x)呈正相关。     

铁和不同形态氮素对玉米植株吸收矿质元素及其在体内分布的影响——Ⅰ.对氮、磷、钾、钙、镁等营养元素的影响

用营养液培养方法研究了铁和两种形态氮素(NO₃^--N和NH₄⁺-N)对玉米植株吸收氮、磷、钾等大量元素和钙、镁等中量元素及其在体内分布的影响。结果表明:与NO₃^--N相比,供应NH₄⁺-N促进了玉米对氮的吸收,在缺铁条件下,降低了对磷、钾、钙及镁的吸收。铁和NH₄⁺-N都显著提高了玉米植株各器官中氮的含量。与NH₄⁺-N处理相比,NO₃^--N处理的新叶中磷含量显著增加,但铁的供应对植物体内磷的含量无显著影响。使用NO₃^--N显著提高了玉米新叶和老叶中钾的含量,根和茎中钾的含量无明显影响。铁的供应降低了新叶和老叶中钾的含量。供铁时,NH₄⁺-N处理的玉米新叶中钙和镁的含量显著低于NO₃^--N处理,而在缺铁时则无显著差异。     

土壤中可变电荷表面磷的解吸特性

本文研究了土壤中可变电荷表面磷的解吸特性。结果表明,磷解吸量与吸附量成正相关,并与直线方程和指数方程拟合。其平均解吸百分数依次为:高岭石(66%)>无定形硅酸铝(60%)>砖红壤粘粒(55%)>>无定形氧化铁(29%)>三水铝石(23%)>>火山灰粘粒(9%)。解吸体系的pH是借对磷酸根质子的解离和表面电荷的影响而制约解吸量。F^-和OH^-离子对磷酸盐化的三水铝石连续解吸的结果表明,磷酸根和氟离子在三水铝石表面的吸附量或剩余量之和均较为接近,这揭示了H₂PO₄^-和F^-离子之间既竞争又相互补充表面空位。它可作为一种区分磷吸附形态和沉淀的定量方法来进一步研究。     

不同有机替代方式下稻田土壤胶体磷流失潜力研究

土壤胶体因具有较大的比表面积及较强的吸附与迁移能力，其所携带的磷（胶体磷）已成为农田磷流失过程中的重要形态。为评估不同有机替代方式下稻田土壤胶体磷（P_coll）的活性和流失潜力，本文依托两种有机肥部分替代化肥（控氮控磷与控氮不控磷）方式下稻麦轮作长期定位试验，探讨了P_coll含量变化、流失风险及其与不同土壤活性磷组分之间的关系。控氮控磷试验（4 a）设有3个处理：不施磷肥（CK）、单施化肥（CF）、猪粪有机肥替代30%化学磷肥（OF）；控氮不控磷试验（24 a）设有3个处理：不施肥（CK）、单施化肥（CF）、猪粪有机肥替代40%化学氮肥（OF）。结果表明：在控氮控磷条件下，有机替代处理较单施化肥处理，土壤有机碳（SOC）、P_coll含量及其流失潜力（LPP）均无显著性差异，胶体钼蓝反应磷占比（R_MRP，MRP_coll/P_coll）显著降低1.76%（P < 0.05）。在控氮不控磷条件下，有机替代处理的土壤P_coll和SOC含量分别为13.08 mg/kg和20.19 g/kg，显著高于单施化肥78%和212.6%（P < 0.05）；较单施化肥，土壤LPP和R_MRP分别显著升高了1.89%和16.05%（P < 0.05）。两种有机替代方式下土壤P_coll与土壤全磷（TP）、真溶解态磷（TSP）、Olsen-P、CaCl₂-P等均呈极显著正相关（P < 0.01）；与土壤有机碳（SOC）在控氮不控磷条件下呈极显著正相关（P < 0.01），在控氮控磷条件下无显著相关性。以上结果表明，较控氮控磷有机替代方式，长期仅控氮的有机肥施用显著增加了土壤有机碳、胶体磷和不同活性磷组分含量，磷流失风险升高。因此，有机肥部分替代化肥养分等量控制是改善农田磷流失可行的施肥方式。     

有机质和陪伴阴离子对土壤吸附Zn的影响

本文研究了土壤有机质和陪伴阴离子对黄棕壤、红壤和砖红壤吸附Zn²⁺的影响。结果表明:土壤有机质含量与吸附Zn²⁺的数量呈正相关;陪伴阴离子对土壤吸Zn²⁺量有显著的制约作用,土壤从ZnCl₂溶液中吸附的Zn²⁺数量高于Zn(NO₃)₂的0.77-1.16倍;△pH值与吸Zn²⁺量呈直线关系。由解吸情况可以判明红壤胶体表面的高能吸附位占的比例明显大于黄棕壤或砖红壤。     

Effects of Organic Anions on Phosphate Adsorption and Desorption from Variable—Charge Clay Minerals and Soil

Effects of citrate and tartrate on phosphate adsorption and desorption from kaolinite,goethite,amorphous Al-oxide and Ultisol were studied.P adsorption was significantly decreased as the concentration of the organic anions increased from 10^-5 to 10^-1 M.At 0.1 M and pH 7.0,tartrate decreased P adsorption by 27.6%-50.6% and citrate by 37.9-80.4%,depending on the kinds of adsorbent.Little Al and/or Fe were detected in the equilibrium solutions,even at the highest concentration of the organic anions.Effects of the organic anions on phosphate adsorption follow essentially the competitive adsorption mechanism.The selectivity coefficients for competitive adsorption can be used to compare the effectiveness of different organic anions in reducing P adsorption under given gonditions. Phosphate desorption was increased by 3 to 100 times in the presence of 0.001 M citrate or tartrate compared to that in 0.02 M KCl solution alone.However,for all the soil and clay minerals studied the amount of P desorbed by citrate or tartrate was generally lower than or close to that of isotopically exchangeable P.The effect of organic anions on phosphate desorption arises primarily from ligand exchange.     

Simulation of the effect of citrate exudation from roots on the plant availability of phosphate adsorbed on goethite

Rhizosphere processes strongly influence the availability of phosphorus (P) to plants. Organic ligands that are exuded from the root surface mobilize phosphorus by dissolution of P minerals or by desorption of adsorbed phosphate. We developed a mechanistic model to study the mobilization of phosphate sorbed on goethite by the exudation of citrate and consequent uptake of phosphate by the root. The use of a model allows the effects of the organic anion and pH on P desorption to be separated. The model is also used to predict concentration profiles developing around the root for phosphate, citrate (with or without accounting for degradation) and pH, providing insight into the processes that occur in the rhizosphere. Results of model calculations show that with larger rates of citrate exudation, greater P availability is predicted. Exudation at a rate of 0.5 μmol citrate m^–1 root day^–1, which is in the range found for P-deficient plants, increased P availability almost 2-fold at fairly large phosphate loading of goethite (1.9 μmol m^–2) and almost 30-fold at small phosphate loading (1.3 μmol m^–2). Competitive adsorption causes a much greater relative increase in the phosphate concentration in solution at small than at large phosphate loading, which explains this result. Simultaneous acidification of the rhizosphere results in a smaller P mobilization than at a fixed pH of 5, as a result of the pH dependence of phosphate adsorption in the presence of citrate. Sorption of citrate increases its persistence against microbial decay, and hence has a positive effect on the mobilization of adsorbed phosphate.     

低分子量有机配体对黏粒矿物吸附苏云金芽孢杆菌的影响

土壤是微生物的理想栖息地,土壤微生物群落组成复杂,数量巨大。1g土壤中可能栖息着上百亿个微生物,其中细菌可达1010个[1]。约80%～90%的土壤微生物寄居于土壤固相表面,如黏土矿物、金属氧化物或有机质表面[2]。细菌与矿物间的相互作用在土壤污染物转化与降解、团聚体形成[3]、矿物风化[4-6]及病原菌运移[7-8]等诸多过程起着关键作用。     

Retention of Ni,Zn and Cd by Si-associated goethite

Synthetic goethite used to study the effects of reaction time and temperature on the pH-dependent sorption of Ni, Zn and Cd was associated with amorphous silica. Ni interacted with dissolved Si and formed a Ni/Si precipitate on the goethite surface. Individual metals added at a concentration of 0.5 μmol g^?1 and sorbed during a reaction period of 504 hours (21 days) at 35°C were extracted by 0.7 M HNO₃ for 14 days. At the end of this period 11,28 and 40 percent of Ni, Cd and Zn, respectively, were not extracted whereas 20 percent of the total Fe content of the goethite and 39 percent of the associated Si were dissolved. During the sorption process metals became immobilized in the goethite particles. This effect can be related to a diffusion of metal ions into micropores. A total mobilization of sorbed metals can only be achieved by a complete dissolution of the goethite. The strong fixation of Ni, Zn and Cd by goethite suggests that additions of this Fe oxide could be used to ameliorate highly contaminated sludges or soils.     

TIME-DEPENDENT SORPTION OF PHOSPHATE BY SOILS AND HYDROUS FERRIC OXIDES

The sorption of inorganic phosphate (P) by soils and hydrous ferric oxides was studied at times up to 192h. An initially rapid decrease in solution P concentration was followed by a much slower decrease between 48 and 192h with soils, Fe gel. and natural goethite, whereas synthetic goethite gave a well-defined equilibrium condition after only 48h. Resolution of the sorption isotherms showed that the increase in P sorption with time involved an appreciable shift of P from a more-physically sorbed form to a chemisorbed form. This was supported by chemical fractionation which showed that NaOH-extractable P was fairly constant with increasing sorption time, whereas the additional sorbed P was extracted by citrate-dithionite-bicarbonate from soils, and by HC1 from Fe gel and natural goethite. These sorbents contained short-range (amorphous) material, whereas synthetic goethite, from which all sorbed P was NaOH –extractable. did not. It is proposed that the time-dependent sorption of P and the associated shift of P to chemisorbed forms, involves the diffusion of P into “structurally porous”, short-range order material.     

SORPTION OF INORGANIC PHOSPHATE BY IRON- AND ALUMINIUM- CONTAINING COMPONENTS

The amounts of inorganic P sorbed by a range of Fe- and Al- containing components varied appreciably and decreased in the order allophane > fresh Al gel > Fe gel pseudoboehmite > aged Al gel > dried Fe gel > Fe-coated kaolinite > haematite > goethite > akaganeite > gibbsite = ground kaolinite > dispersed kaolinite. Al gel sorbed 30 to 70 times more P than gibbsite, and Fe gel sorbed approximately 10 times more P than its crystalline analogues (haematite, goethite. and akaganeite). Despite large differences in the extent of P sorption, the form of the isotherm was essentially the same for each sorbent. The ability of freshly-prepared Al gel suspensions to sorb P decreased with ageing, a property not shown by Fe gel. Drying of Fe gel at 80°C, however, caused an approximately 4-fold decrease in P sorption. Precipitation of Fe gel (2% Fe) on the surface of kaolinite increased P sorption by a factor of 10. The occurrence of Fe gel as a coating apparently presents more sorption sites to solution per unit weight of Fe gel than Fe gel alone. A linear relationship (r= 0.98) was obtained between the amount OH^? sorbed per unit increase in pH value (‘hydroxyl buffering’) and the overall P sorption maximum for each sorbent. Hydroxyl buffering provided a better index of P sorption potential than specific surface area. Except for the crystalline Fe sorbents, isotherms obtained by plotting fractional sorption saturation against final solution P concentration for the sorbents were essentially coincident with those for several contrasting soils. For crystalline Fe components a lower relative amount of weaker sorption, as opposed to chemisorption, of the overall sorption maximum was obtained. Differences in the extent of P sorption. however, appear to be primarily related to the number of functional M-OH groups presented at the solid-solution interface.     

有机酸根与铝氧化物表面吸附磷的解吸

研究了有机酸根离子与合成铝氧化物表面吸附磷解吸的相互关系。结果表明:（1）有有机酸时比无有机酸时吸附的磷具有更高的解吸率，无草酸且加磷pH为4时，0.01molL-1KCI对磷的解吸率最低，草酸与磷共存且pH为6时磷的解吸率最高;（2）高浓度有机酸可解吸低浓度有机酸难解吸的磷，草酸难解吸的磷可为等浓度的柠檬酸极解吸;（3）不同浓度草酸和柠檬酸对铝-草酸复合物吸附磷的解吸率比对Al（OH)x的低，而对铝-柠檬酸复合物吸附磷的解吸率则比对Al（OH）x的高;（4）柠檬酸对铝-磷复合物中磷的解吸量随柠檬酸浓度升高而增大。这些结果证明，有机酸对铝氧化物吸附磷的解吸机理包括配位交换和溶解，有机酸可促进磷的解吸，提高磷的有效性。     

有机酸对高岭石, 针铁矿和水铝英石吸附镉的影响

Effects of organic acids （oxalic, acetic, and citric） on adsorption characteristics of Cadmium （Cd） on soil clay minerals （kaolinite, goethite, and bayerite） were studied under different concentrations and different pH values. Although the types of organic acids and minerals were different, the effects of the organic acids on the adsorption of Cd on the minerals were similar, i.e., the amount of adsorbed Cd with an initial solution pH of 5.0 and initial Cd concentration of 35 mg L^-1 increased with increasing concentration of the organic acid in solution at lower concentrations, and decreased at higher concentrations. The percentage of Cd adsorbed on the minerals in the presence of the organic acids increased considerably with increasing pH of the solution. Meanwhile, different Cd adsorption in the presence of the organic acids, due to different properties on both organic acids and clay minerals, on kaolinite, goethite, or bayerite for different pHs or organic acid concentrations was found.     

Competitive adsorption between phosphate and carboxylic acids: quantitative effects and molecular mechanisms

The competitive adsorption at the water‐goethite interface between phosphate and a carboxylic acid, either oxalate, citrate, 1,2,3,4‐butanetetracarboxylic acid (BTCA), mellitate or Suwannee River Standard Fulvic Acid 1S101F (FA), was investigated over a wide pH range (3–9) by means of batch experiments and attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy. The quantitative results from the competitive adsorption measurements show that the efficiency of the organic acids in competing with phosphate was in the order oxalate < citrate < BTCA ≅ FA < mellitate. Oxalate showed no detectable effect, whereas the effect in the mellitate system was strong, and the aggregative results indicate that an increasing number of carboxylic groups favours competitive ability towards phosphate. The infrared spectroscopic results show conclusively that competition for goethite surface sites between carboxylic acids and phosphate is not a ligand‐exchange reaction between inner‐sphere surface complexes. Instead, ligands capable of multiple H‐bonding interactions are required to out‐compete and desorb surface complexes of phosphate. The fact that partially protonated organic acids are the most efficient emphasizes the importance of both H‐accepting carboxylate groups and H‐donating carboxylic acid groups for the competitive effect.