A column perfusion test to assess the kinetics of nutrient release by soluble,sparingly soluble and coated granular fertilizers

In recent years, innovations in fertilizer research have principally been in the design of products to supply more timely plant nutrients and mitigate detrimental losses to the environment. In the development of these fertilizers, a laboratory method to comparatively screen a large number of formulations for the rate of nutrient release is a critical first step in formulation optimization to significantly reduce time spent on pot and field trials, reducing costs considerably. Currently, given the absence of a standard laboratory method for all fertilizers, adaptions of a method for coated fertilizers from the International Organization for Standardization (2017) ISO 21263 and other column tests are being used which are often complex and/or require manual sampling which can be laborious, time consuming and costly. The method presented here evaluates the dynamic release in real time by continuously perfusing samples in columns utilizing an automated sample accumulation system for short‐term and long‐term release studies and eliminates the need for soil/sand packing of columns. Mass balance is accounted for by analysing the residue after dissolution and the amount released is expressed as a % of the total nutrient content in the product. This method is reliable, uncomplicated and cost‐effective and has been used to test uncoated soluble fertilizers, nanofertilizers, fertilizers with newly developed coating technologies and other slowly soluble fertilizers, to assess the effect of variables like coating chemistry and thickness, fertilizer composition or fertilizer particle size on release rate.     

保水剂与肥料互作及保水缓/控释肥料研究展望

保水剂在农业上的作用日益重要,肥料与保水剂一体化使用是水肥调控的重要技术,是肥料研究的国际前沿。保水剂是吸水量超过自身重量数百倍以上的亲水性高聚物。保水剂一般分为天然的,合成的及半合成的。保水剂与肥料可以通过物理混合、包膜或化学合成三种方式结合为一体化的保水缓/控释肥料。保水剂具有吸水吸肥功能,保水剂可吸附大量中性分子,对阳离子养分也有较强吸附作用,对阴离子养分吸附弱。肥料种类与盐浓度影响保水剂的吸附作用与膨胀能力。保水缓/控释肥料在土壤中对肥料养分有延迟释放作用。保水缓/控释肥料可改善土壤持蓄水分和水肥交互作用,促进植物对养分的吸收和作物增产。保水缓/控释肥料发展方向是包膜和化成保水缓/控释肥料。保水缓/控释肥料湿润及养分控释机理研究也需要加强。     

高温-超低温处理对控释肥氮素释放特性的影响

采用水培和土培方法,探讨了2种组合的高温-超低温处理对MEISTER 180氮素释放特性的影响。结果表明,55℃处理期平均养分溶出率（η△t）为6.6%~8.9%;超低温处理期平均养分溶出率（η△t）为0.1%~0.6%。高温-超低温处理后MEISTER 180水中和土中氮素释放均呈直线型模式,相关系数R2在0.8552~0.9505之间;水中和土中养分溶出率比值变动范围在1.0~1.3之间,表明氮素释放受水分影响小,高温-超低温处理未改变MEISTER 180释放模式。     

Cation treatment and drying‐temperature effects on nonylphenol and phenanthrene sorption to a sandy soil

The objective of this study was to investigate the effects of mono‐ and polyvalent cations on sorption of the two hydrophobic compounds nonylphenol (NP) and phenanthrene (Phe). To this end, exchange sites of a sandy soil were saturated with either Na⁺, Ca²⁺, or Al³⁺ and excess salts were removed by washing. The samples were then sterilized and either stored moist, dried at room temperature, or at 20°C, 60°C, or 105°C in a vented oven. Saturation with Na⁺ led to an increase of dissolved organic C (DOC) concentration in the soil water extracts, whereas the polyvalent cations Ca²⁺ and Al³⁺ decreased it. The ¹H‐NMR relaxometry analyses showed that Al³⁺ restricted the mobility of water molecules that are confined within the SOM structure to a higher extent than Ca²⁺ or Na⁺. According to contact‐angle (CA) analyses, cation treatment did not significantly change the wetting properties of the samples. Batch sorption–desorption experiments showed no clear salt‐treatment effects on the sorption and desorption equilibria or kinetics of NP and Phe. Instead, the sorption coefficients and sorption hysteresis of NP and Phe increased in dry soil. With increasing drying temperature the CA of the soils and the sorption of both xenobiotics increased significantly. We conclude that structural modifications of SOM due to incorporation of polyvalent cations into the interphase structure do not modify the sorption characteristics of the soil for hydrophobic compounds. Instead, increasing hydrophobization of organic soil constituents due to heat treatment significantly increased the accessible sorption sites for nonpolar organic compounds in this soil.     

松香甘油酯包膜材料对尿素缓释性的影响

该文以松香甘油酯为包膜材料,生产包膜尿素,并利用盆栽土壤试验法,研究以松香甘油酯为包膜材料的包膜尿素缓释性能。结果表明：C=5%其初溶出率均为12.9%。用LOGISTIC生长曲线模型进行模拟,得到涂层覆盖率C=5%时,其最大养分释放量为96%,养分释放期为146 d;涂层覆盖率C=8.1%时,其最大养分释放量为97%,养分释放期为194 d,这表明：控制涂层覆盖率,可控制肥料释放周期;松香甘油酯为包膜材料的选用开辟了新的途径。     

改性聚丙烯酸酯包膜控释肥料的控释性能研究

针对应用流化床包衣设备进行水溶性高分子聚合物包膜肥料中试生产中存在的问题,研究了交联剂用量对膜材料表面结构与疏水性能的影响,以及不同后处理工艺对改善包膜肥料控释性能的作用。结果表明,以水溶性高分子聚丙烯酸乳液为主成分的包膜材料中添加交联剂(氮丙啶)的比例由1%(质量百分数,下同)增加至2%,肥料包膜表面结构变得更加平整致密,疏水性能也有所增强,控释效果显著提升。在40℃静水浸泡的9 d时间内前者释放了90%以上的养分,而后者仅释放了约40%的养分。不同后处理工艺对增强包膜肥料的控释性能作用不一。烘箱加热的效果远好于微波处理,且当交联剂添加比例较低(0.3%)时,在一定范围内(60℃~80℃)升高后处理温度,包膜肥料的控释性能显著增强。而当交联剂添加比例增至1%以上时,升温对其控释性能几乎无影响。     

Formulation,synthesis and characterization of boron phosphate (BPO4) compounds as raw materials to develop slow‐release boron fertilizers

We investigated the use of boron phosphate (BPO₄) as a slow‐release boron (B) source. Boron phosphate compounds were synthesized by mixing boric acid (H₃BO₃) and phosphoric acid (H₃PO₄) and heating at temperatures of 25 to 1000°C for 1 or 24 h. X‐ray diffraction (XRD) patterns and chemical analysis confirmed the formation of BPO₄. The crystallinity of these compounds increased with increasing temperature and heating time. The compounds synthesized at 300°C or less were hygroscopic and clumped together, while those synthesized at 500 to 1000°C were non‐hygroscopic and free‐flowing. The solubility of these compounds was assessed at different pH and P concentrations, and compared to the solubility of ulexite and colemanite. The solubility of the BPO₄ compounds decreased with increasing synthesis temperature and with decreasing pH. The solubility and the kinetics of B release from BPO₄ compounds synthesized at 500 and 800°C were slower than for most commonly used B sources. Given their slow dissolution, the BPO₄ compounds may have potential to continuously supply B to crops in environments where B leaching is a problem. The compounds synthesized at 500 and 800°C show potential for co‐granulation with macronutrient fertilizers such as mono‐ammonium phosphate to produce slow‐release B‐enriched granules.     

不同粒径生物炭包膜尿素缓释肥性能及缓释效果

为探究生物炭粉包膜处理对尿素缓释效果的影响,该研究以不同粒径稻壳生物炭粉为包膜材料,对尿素颗粒进行不同层数包膜处理,分别制备了3种生物炭包膜尿素缓释肥C_1(0.15 mm生物炭粉包膜)、C_2(内层0.15 mm,外层0.25 mm生物炭粉包膜)和C_3(内层0.15 mm,中层0.25 mm,外层0.425 mm生物炭粉包膜),并对生物炭包膜尿素缓释肥性能及缓释效果进行了分析研究。研究结果表明3种生物炭包膜缓释肥粒径主要分布在2.90～4.80 mm,随着包膜层数的增加,包膜缓释肥粒径随之增大,C_2和C_3粒径显著高于C_1(P0.05)。C_1、C_2和C_3的抗压强度为20.40～48.00 N,满足工业生产需求。与C_1和C_2相比,C_3颗粒表面较光滑,切面具有致密且孔隙结构丰富的层状结构,吸水倍率最小(1.69),耐水性也显著优于C_1与C_2(P0.05),氮元素缓释效果优于C_1与C_2。综上可以看出,3层包膜尿素缓释肥膜壳强度高于单层和双层包膜尿素缓释肥,通过控制不同膜层生物炭的孔隙结构和孔径,减缓水分的渗入及养分的流出过程,缓释效果突出,为生物炭包膜缓释肥的开发应用提供一个新技术路径。     

Nitrogen release from plant‐derived and industrially processed organic fertilizers used in organic horticulture

As a consequence of the BSE crisis, alternatives for fertilizers derived from animal residues are being sought for use in organic horticulture. Grain legumes (milled seeds of pea, yellow lupine, and faba bean) and organic fertilizers of industrially processed plant and microbial residues (Maltaflor®‐spezial, Phytoperls®, Agrobiosol®, Rizi‐Korn) were investigated as to their suitability as a replacement fertilizer. With four soils, incubation studies were conducted to determine net N mineralization of the organic fertilizers, and pot experiments were used to measure the apparent N utilization by perennial ryegrass. The objectives of this study were (1) to determine simple fertilizer characteristics that describe their N release and (2) to compare the suitability of both experimental setups to predict fertilizer N release. At the end of all experiments, net N mineralization and apparent N utilization from Rizi‐Korn was highest compared to all the other organic fertilizers, while pea performed relatively poor. This differentiation between the fertilizers developed during the first 2 weeks. Nitrogen release from the organic fertilizers as described by net N mineralization or apparent N utilization was significantly related to the N content of the fertilizers. Different soils modified this relationship. Two industrially processed fertilizers (Phytoperls®, Agrobiosol®) could not be included into a generalized relationship because N release from these fertilizers was low compared to their N content. It is discussed that the quality of fertilizer C and N affected the N release from the fertilizers. Both experimental setups, incubation and pot experiments, were suitable to describe the release of plant‐available N from the organic fertilizers. However, N release of fertilizers with a low net N mineralization in the incubation experiments was underestimated compared to plant N uptake of ryegrass in the pot experiments. It is concluded that the N content of organic fertilizers indicates, but not predicts their N release.     

保水缓/控释肥料的研究进展

肥料与保水剂复合一体化使用是水肥调控的重要技术，是肥料研究的国际前沿。该文主要对保水剂与化肥的复合方式与工艺，保水剂与肥料养分相互作用及其研究方法，以及保水及保水肥料应用的水肥效应方面的进展进行综述，并指出了保水缓/控释肥料研究存在的问题和今后努力的方向。保水剂与肥料可以通过物理混合(吸附或造粒)、包膜或化学合成3种方式结合为材料与功能复合一体化的保水缓/控释肥料，包膜和化学合成是高养分含量保水缓/控释肥料制备的先进工艺。肥料或盐影响保水剂的吸水膨胀及吸附作用，因肥料及盐的种类和离子电价而异。7 d溶解量法、土壤淋洗法及土壤培养法等是研究保水剂及保水缓释肥料养分吸附解吸的常用方法。保水剂或保水缓/控释肥料对一些养分的缓释作用报道基本一致，对土壤水分改善作用存在不一致的报道，与高盐含量和保水剂用量有关。保水缓/控释肥料今后发展方向应加强养分含量与吸水倍率指标标准、保水材料及其与肥料复合机制的创新、以及湿润及养分控释机理的研究，还应加强中试及产业化技术开发研究。     

控释肥在基质栽培中的养分淋溶及其对基质理化性质的影响

无土栽培是设施农业中广泛采用的先进技术,能有效克服土壤连作障碍,具有省水、省肥、省工等土壤栽培难以比拟的优势,控释肥在基质栽培中的应用,使无土栽培技术的发展前景更加广阔。本文通过无土栽培试验,研究了控释复合肥在基质中的养分变化规律及其对基质理化性质的影响。研究结果表明,控释肥氮、磷、钾、铁和锌的释放规律基本一致,且养分的控制释放减少了养分流失,降低了基质中的盐分浓度,与普通速效肥相比更具有安全性;控释肥明显改变了基质的容重、孔隙度,改善了基质的水气状况,从而为作物的生长提供了良好的生长环境。     

膜特性对包膜控释肥养分控释性能的影响

为了研究膜特性对包膜控释肥养分控释性能的影响,该文通过膜的拉伸试验、扫描电镜和养分水中溶出率法对P1和P2树脂膜（不同包膜比率,不同添加剂含量）的机械性质、微观结构和养分控释特性进行了研究,结果表明,P1树脂膜机械性能较差,易发生龟裂现象,且通透性较大;P2树脂膜机械性能较好,但通透性较差;仅通过改变包膜比率不能达到改变两种膜的控释性能的目的。在不同包膜比率两种膜中分别添加适量的高分子疏水物质和可降解改性淀粉,可明显改善膜壳的机械性质、微观结构并起到了对养分释放速率的调控作用。两种膜材料包膜的控释肥料的控释性能均可通过改变各自的包膜比率和添加物的比例来调控,其关系可用函数关系模拟,且拟合度均达到显著水平。     

丙烯酸树脂包膜尿素肥料研制及其控释效果

采用丙烯酸树脂为包膜材料,以NBPT（N-丁基硫代磷酰三胺）和DCD（双氰胺）为生化抑制剂,利用流化床对尿素进行涂层生化抑制剂及包膜,制备4种包膜肥料,对这些包膜肥料在水中的控释效果进行了研究。结果表明,采用此技术制备的包膜肥料,表面成膜完整,包膜物质在成膜时分布均匀、与尿素肥心接合紧密,表面光滑。NBPT和DCD与肥心结合严密,包膜层紧覆于抑制剂的外表。包膜可有效控制尿素的溶出,在水中的控释时间为19～30d。初期溶出率远远小于15％,微分溶出率基本上在0．25％～2．5％之间;在水中尿素累积溶出特征符合一元二次方程模型,尿素释放曲线呈“S”形。     

Ceramic Aggregate Sorption and Desorption Chemistry: Implications for Use as a Component of Soilless Media

Ceramic aggregates (Turface® and Profile®) are common soilless media components, but their sorption/desorption chemistry is poorly understood. We investigated: labile (readily desorb-able or readily plant-available) ion concentrations; the effect of rinsing and soaking pretreatments on labile ions; sorption of applied nutrients; and nutrient uptake from the aggregates by plants. Variability in labile ions was extremely high among bags of aggregates. Manganese, boron, magnesium, calcium, sulfur and potassium were most likely to desorb in excess for plants. Phosphorus, iron, copper and zinc were sorbed by the aggregates; only copper was found nearly deficient in plant tissue. Rinsing and soaking pretreatments adjusted labile ions to more suitable concentrations for plants. However, growth data suggested a worst-case scenario of high levels of labile ions may not be mitigated by these pretreatments. With frequent leaching after planting or where the aggregates are a minor component of media, excessive nutrient uptake would likely be limited.     

Comparison of slow‐release nitrogen yield from organic soil amendments and chemical fertilizers and implications for regeneration of disturbed sites

Soil amendments are commonly used to regenerate nutrient levels on disturbed construction sites or mined lands prior to revegetation. Management of nitrogen (N) inputs to the degraded substrates is difficult because the low level of ambient fertility on disturbed substrates requires large total N inputs to sustain revegetative growth, but it also requires low N bioavailability in order to avoid weedy invasion and eutrophication of local watersheds. Commonly available soil amendment materials have a wide variety of N contents and release rates, making specification of appropriate N amendments difficult. We compared N release rates of a variety of organic‐based soil amendments and chemical fertilizers in long‐term aerobic incubation chambers in the lab and at a field revegetation site. The N release rate from these amendments fell into four general groups: (1) rapid N release from soluble chemical fertilizer formulations, (2) longer, controlled N release from chemical‐based, slow‐release formulations, and a two‐phase release pattern (rapid initial phase, slower second phase) from (3) organic‐based blends, as well as (4) unsupplemented municipal yard‐waste composts. The release rates from organic‐based amendments were about three times faster in the 30°C laboratory incubations than in the cool, moist winter growing season at a field site in the Central Valley of California. Relative rates of N release can be compared between amendment materials to help guide selection of N amendments, according to the plant‐growth goals of the revegetation project. Copyright © 2006 John Wiley & Sons, Ltd.     

水肥调控技术及其功能性肥料研究进展

综述水肥调控的有关技术,以及以高吸水性树脂 (super absorbent polymer,SAP) 为保水、缓/控释材料制备保水型缓/控释肥料的研究进展,为今后此类肥料的开发、应用提供依据。水分和养分是限制我国旱地农业可持续发展的主要因子,以肥调水,以水促肥,充分发挥水肥的协同效应是提高水肥利用率的关键。目前,水肥调控 (耦合) 技术的实施主要通过农艺措施和施肥灌溉技术来完成。近年来,随着SAP性能的不断改善和使用的普及,人们对SAP在吸水保水的同时,对土壤肥料养分的保持和缓释作用开始给予了重视,以SAP为保水、缓释材料的保水型缓/控释肥料的研究成为水肥调控研究的热点。SAP与一般聚合物不同之处是它具有高度亲水性,聚合物的骨架是一个适度交联的网状结构,进入树脂分子内的养分离子或分子可以以各种结合形式被暂时固定而延缓了养分的释放。土壤中可溶性盐对SAP吸水性能有重要影响,但尿素分子影响甚小。保水型缓/控释肥料可通过养分负载、复混或包膜等工艺制备。保水型缓/控释肥料是水肥调控 (耦合) 技术、化学制剂保水节水技术和肥料缓/控释技术的综合运用和物化的载体,兼具吸水、保水和养分缓/控释功能,实现水肥在同一时空条件下的一体化调控,同时提高水分和肥料的利用效率,在农业、林业、环境修复、生态工程等领域具有广阔的应用前景。未来工作是进一步寻求合适的SAP制造原料和工艺,降低成本;应用分子设计,改善SAP的结构,提高生物降解性,控制盐分的不利影响,提高肥料的吸水、保水和对养分的缓释性能;加强养分释放机理和不同于普通缓/控释肥料评价方法的研究。     

包膜控释肥料养分释放率快速测定方法的研究

包膜控释肥料养分释放率的快速测定是控释肥质量检测和制定评价标准的关键。快速测定方法可以在较短时间内,推测和评价控释肥料的养分释放速率的快慢及释放期的长短。本研究对4种不同包膜控释肥料在25℃温度条件下的静水释放过程进行了测定,并应用100℃快速浸提化学实测法的测定结果与之拟合,找出两者相同养分释放量的时间对应关系方程,并对方程进行了检验和评价;同时,还对100℃温度条件下快速浸提液进行了电导率法(简便方法)的测定。结果表明,4种不同包膜控释肥料的相同养分释放量与时间对应关系方程的拟合度均达到极显著水平;在100℃温度条件下,快速浸提测定法能在较短的时间内准确测定包膜控释肥料的养分释放率,释放期为36～个月的包膜控释肥,在104～8.h就可初步测定出养分释放期;在25℃释放期为6个月的控释肥,100℃快速浸提测定的养分释放期的最大误差为10.d(5.6%);100℃快速浸提电导率法亦可简便快速的测定出包膜控释肥的养分释放率,其对养分释放期为6个月的包膜控释肥料预测值的最大误差为15.d(8.3%)。     

Hot‐Water Solubilities and Water Sorptions of Resistant Starches at 25°C

Resistant starches (RS) were prepared from wheat starch and lintnerized wheat starch by autoclaving and cooling and by cross‐linking. Heat‐moisture treatment also was used on one sample to increase RS. The experimental resistant starches made from wheat starch contained 10–73% RS measured as Prosky dietary fiber, whereas two commercial resistant starches, Novelose 240 and 330, produced from high‐amylose maize starch, contained 58 and 40%, respectively. At 25°C in excess water, the experimental RS starches, except for the cross‐linked wheat starch, gained 3–6 times more water than the commercial RS starches, and at 95°C gained 2–4 times more. Cross‐linked RS4 wheat starch and Novelose 240 showed 95°C swelling powers and solubilities of 2 g/g and 1%, and 3 g/g and 2%, respectively. All starches showed similar water vapor sorption and desorption isotherms at 25°C and water activities (a_w) < 0.8. At a_w 0.84–0.97, the resistant starches made from wheat starch, except the cross‐linked wheat starch, showed ≈10% higher water sorption than the commercial resistant starches.     

缓释复合肥养分释放特性和黄连生物效应研究

采用连续恒温培养和大田试验研究了4种缓释复合肥在种植黄连的土壤(森林黄棕壤)中的养分释放特性及其对黄连产量和药用品质的效应。结果表明,20℃恒温模拟条件下缓释复合肥氮、磷、钾养分缓释性能较佳,3种养分释放的动力学过程可用Elovich方程St=a+blnt、双常数方程lnSt=a+blnt和抛物线扩散方程St=a+bt0.5表征,各方程参数b值均可用于描述缓释复合肥氮、磷、钾养分释放速率。在田间试验中4种缓释复合肥极显著提高3～5年生黄连产量,大幅度提高黄连小檗碱和生物碱产量,并以SRF3、SRF2和SRF13种缓释复合肥的效应大。     

Immobilization of heavy metals in soils amended by nanoparticulate zeolitic tuff: Sorption‐desorption of cadmium

Immobilization of Cd in contaminated soil is a technique to improve soil quality. Zeolites are potentially useful additives to bind heavy metals. This study examines the influence of decreasing the grain size of raw zeolitic tuff to the nano‐range on Cd sorption‐desorption isotherms in a sandy soil. The aim was to evaluate the feasibility of using nanoparticulate zeolitic tuff as a sequestering agent for Cd in soil. Sorption and desorption of Cd on zeolitic nanotuff was investigated in batch experiments. The sandy soil was amended with zeolitic nanotuff, synthetic Al oxide nanoparticles, or raw zeolitic tuff. After a 48 h sorption step, three desorption steps were induced using the sequential dilution method. The measured sorption‐desorption data were adequately described by the Freundlich equation. A nonlinear two‐stage one‐rate model matched well with measured Cd sorption‐desorption isotherms of zeolitic nanotuff, raw zeolitic tuff, Al oxide nanoparticle, and control soil. The batch experiments demonstrated the strong influence of pH on Cd sorption. Zeta‐potential measurements of zeolitic nanotuff indicated that electrostatic interaction was important for sorption. Soil amended with zeolitic nanotuff showed the lowest hysteresis index based on the differences obtained from sorption‐desorption isotherms regarding the amount of Cd sorbed. The index decreased with increasing metal concentration. For soil amended with nanoparticulate zeolitic tuff, the estimated Freundlich coefficient was 4 orders of magnitude higher than in the control soil and 2 orders of magnitude higher than the soil amended with raw zeolitic tuff. In addition, this sorbent decreased the amount of Cd released after three desorption steps by up to 12 and 7 times compared to the control soil and the soil amended with raw zeolitic tuff, respectively. The effect on Cd sorption of grinding the raw zeolitic tuff to the nanorange was considerably more pronounced than the effect of raw zeolitic tuff.