农用生物炭研究进展与前景

受自身理化性质的影响,普通生物炭对磷的吸附能力较差。本研究尝试通过铁改性提升生物炭的磷吸附能力,以增强磷的固储能力,减轻土壤磷流失带来的环境风险。

供试生物炭包括核桃壳炭(WSB)、水稻秸秆炭(RSB)和木质炭(WB)。将10 g生物炭浸泡于1 mol/L HCl中1 h,用蒸馏水洗涤至滤液呈中性后烘干,然后加入到1 mol/L的FeCl₃溶液中,设置铁与生物炭的质量比分别为0.28、0.56、0.84,经静置、过滤、烘干、煅烧后,得到铁改性生物炭,分别记为WSB-0.28、WSB-0.56、WSB-0.84、RSB-0.28、RSB-0.56、RSB-0.84、WB-0.28、WB-0.56、WB-0.84。采用扫描电子显微镜、能谱仪、傅立叶红外光谱仪、X射线衍射仪、全自动比表面积、孔径测试仪和元素分析仪分别对改性生物炭进行表征测定,并分别以2%、4%、6%的比例 (质量比) 添加至土壤中进行磷的吸附解吸试验,选取磷调控能力较好的生物炭进行矮牵牛栽培试验。

Fe₂O₃成功地负载到3种生物炭表面,改性后生物炭的吸附位点显著增多,特别是WSB-0.28对磷的吸附能力显著高于WSB。土壤对磷吸附量随铁改性生物炭添加量增加而增加,在相同添加量下,土壤磷吸附量排序为铁改性水稻秸秆炭>铁改性木质炭>铁改性核桃壳炭 (WSB-0.28除外),而铁改性木质炭对土壤磷的解吸量和解吸率高于其他生物炭。盆栽试验结果表明,富磷铁改性核桃壳炭可增加矮牵牛幼苗根、叶生物量,并提升叶片叶绿素含量及开花量。

铁改性可提升生物炭对磷的吸附能力,增强土壤固磷作用,提高土壤磷素供给,促进植物生长。因此,铁改性生物炭可作为一种新型炭基缓释肥料应用于城市绿地土壤中,固磷增效,减轻土壤磷流失的环境风险。

     

Proton consumption with phosphate adsorption on amorphous fe(iii) hydroxide

Proton consumption with phosphate adsorption on amorphous Fe (III) hydroxide (am-Fe(OH)₃) was compared between two different pH-controlled conditions in a 0.1 mol dm^-3 NaClO₄ solution at initial pH values of 5.50 and 4.50, at 298±0.005 K.

The number of protons caused by phosphate dissociation was subtracted from the total number of protons consumed, then the amount of surface OH groups released by the ligand exchange reaction were determined. When a sequential acid titration by a pH-stat maintained pH values of the systems at initial pH values, the percentage of OH groups released during the ligand exchange reaction was almost constant, 29–37%. When the pH values of the systems increased with phosphate adsorption, the percentage of OH groups released by the ligand exchange reaction varied from -4.3 to 33%. The difference in the proton migration between the two pH-controlled conditions not only depended on the phosphate dissociation, but on the difference in the adsorption mechanism, i.e. the ratio of ligand exchange with OH groups to total phosphate adsorption.     

Effects of Rice Husk Ash and Bagasse Ash on Phosphorus Adsorption and Desorption in an Alkaline Soil under Wheat–Rice System

Rice husk ash (RHA) and bagasse ash (BA) are available in large quantities in South Asian countries growing rice and sugarcane. Land application of RHA and BA is likely to influence chemistry of soil phosphorus (P) and thereby P adsorption and desorption. Laboratory studies were carried out to investigate the short-term and long-term effects of RHA and BA application on P adsorption and desorption in an alkaline soil under a wheat–rice system. Addition of RHA or BA (10 Mg ha^?1) resulted in a significant decrease in P adsorption compared to the control. The decrease in P adsorption was lower when RHA and BA were applied to either rice or wheat as compared with when applied to both the crops. The BA was more effective in reducing P adsorption than RHA because of its greater P concentration. Fresh addition of RHA and BA at 1% (dry-weight basis) showed a small effect on P adsorption as compared to their long-term application. The Frendulich isotherm equation gave better fit with the experimental data than the Langmuir equation and is reliable to describe the P quantity/intensity relationships of this soil as affected by the additions of RHA and BA. The P-adsorption capacities (revealed from the Langmuir isotherms) of the unamended control, RHA, and BA (applied to both wheat and rice) were 256, 313, and 385 mg kg^?1, respectively; the corresponding bonding energies for the three treatments are 0.0085, 0.0041, and 0.0026 L kg^?1, respectively. Desorption of P was minimum in the control plots and maximum with BA followed by RHA, especially when applied to both the crops.     

Effects of Long-Term Fertilization on the Form of Inorganic Phosphorus and the Characteristic of Adsorption and Desorption in Black Soil

Changes of inorganic phosphorus forms and the characteristics of phosphorus adsorption and desorption were studied under a long-term fertilization experiment in black soil. Results showed that the forms of inorganic phosphorus ranged as O–P < Ca₂–P < Ca₈–P < Al–P < Ca₁₀–P < Fe–P. Therefore, Fe–P was the main inorganic phosphorus form in this study. The capacity of phosphorus adsorption with phosphate treatments was higher than with no-phosphorus treatments. The optimal fitted equation was the Langmuir equation. Phosphorus desorption was related to the binding energy. Positive correlation between phosphorus adsorption and desorption without phosphorus addition was found; however, negative correlations among the phosphate treatments had been observed.     

不同生物质炭对棕壤中磷素吸附解吸的影响

为了减少土壤磷素流失,提高磷肥利用效率,探究不同生物炭对棕壤中磷素吸附解吸行为的影响规律,以水稻秸秆、玉米秸秆和花生壳为原材料,利用限氧升温炭化法制备生物炭,通过批量吸附实验研究了生物炭种类和生物炭添加量对棕壤磷吸附解吸的影响。结果表明：水稻秸秆生物炭在添加量为0.4%时显著提高棕壤对磷的吸附量,花生壳生物炭和玉米秸秆生物炭则显著降低棕壤对磷的吸附量;等温吸附曲线表明,不同生物炭均未改变等温吸附曲线的变化趋势,均可用Langmuir方程和 Freundlich 方程进行描述(R²>0.93),其中 Langmuir 方程拟合效果更好,不同处理对磷的理论吸附量大小顺序为：水稻秸秆生物炭+棕壤>棕壤>花生壳生物炭+棕壤>玉米秸秆生物炭+棕壤;吸附动力学实验表明,不同生物炭均未改变磷吸附动力学曲线的变化趋势,在所有动力学模型中,准二级动力学模型最适合描述土壤对磷的吸附行为(R²>0.99),其次为准一级动力模型(R²>0.99)和Elovich动力学模型(R²>0.88);三种生物炭均显著促进棕壤对磷的解吸,当生物炭添加量为≥0.2%时,水稻秸秆生物炭、玉米秸秆生物炭和花生壳生物炭,分别可提高棕壤对磷的解析率50%、70%和90%以上。由此可见,不同生物炭可提高棕壤对磷素的供应和利用,水稻秸秆生物炭在减少棕壤磷素流失、保护生态环境方面具有更大的应用价值。     

不同人工湿地基质对磷的吸附性能研究

通过基质磷素吸附动力学、等温吸附以及基质饱和吸附后磷素解吸实验,研究陶瓷滤料、红泥、水洗砂、炉渣4种人工湿地基质净化磷素的效果,评价其基质磷素饱和吸附后磷素解吸可能造成的二次污染风险。结果表明,在溶液磷（P）浓度为5-150mg·L·^-1条件下,Langmuir和Freundlich等温吸附方程均能很好地描述陶瓷滤料和红泥两种基质的磷素吸附过程,陶瓷滤料用Langmuir方程比Freundlich方程的拟合程度更好,红泥则相反。4种基质对磷素的吸附量顺序依次为红泥〉陶瓷滤料〉炉渣〉水洗砂。从磷素的解吸率来看,4种基质释磷顺序依次为炉渣〉水洗砂〉陶瓷滤料〉红泥,水洗砂和炉渣吸附磷素后的解吸率较高,其他两种基质磷素解吸的比例很低。综合评价,陶瓷滤料更适合作为人工湿地污水除磷的基质。     

不同磷浓度处理暗棕壤对Zn2+吸附解吸行为的研究

通过等温吸附试验,研究不同磷含量处理暗棕壤对Zn2+的吸附解吸行为,结果表明:(1)随平衡液中Zn2+浓度的增加,3种处理暗棕壤对Zn2+的吸附作用均表现为:低浓度下(0～100 mg/L),吸附量增加迅速,随着浓度升高(100～150 mg/L),吸附量变缓并渐趋平衡,含磷量高的土壤吸附Zn2+的量较高。(2)Freundlich、Langmuir和Temkin方程均能很好描述Zn2+在3种不同磷含量暗棕壤上的吸附等温线,拟合效果依次为Freundlich>Langmuir>Temkin。经参数计算,较高磷含量有利于提高暗棕壤的最大吸附量和土壤对Zn2+的缓冲容量,而磷含量不同对Zn2+在暗棕壤上的吸附力没有太大影响。(3)3种不同磷含量处理暗棕壤吸附量与解吸量关系图形状相似,呈高度线性相关,均表现为暗棕壤对Zn2+的解吸量随吸附量的增加而增加,磷含量较高土壤有利于Zn2+的固定且不易解吸。     

四川盆地丘陵区农田土壤对磷的吸附与解吸特征

研究了四川盆地丘陵区典型水田和旱地土壤对磷的吸附与解吸特征,并讨论了吸附-解吸参数与土壤基本理化性质的关系。结果表明,不同pH的农田土壤对磷的吸附和解吸均存在显著差异,土壤对磷的吸持能力表现为中性土壤〉酸性土壤〉石灰性土壤,中性有利于土壤吸附磷;水稻土对磷的最大吸附容量（Qm）和最大缓冲容量（MBC）高于紫色土,而临界平衡磷浓度（EPC0）和解吸率（b）低于紫色土。农田土壤对磷的吸附与解吸参数还受土壤理化性质的影响,Qm和MBC与有机质含量、无定形铁（Fe-ox）含量呈极显著正相关（P〈0.01,n=6）;吸附常数（K）与有机磷含量呈显著负相关（P〈0.05,n=6）;EPC0与土壤pH、CaCO3含量呈显著负相关,与有机磷含量呈显著正相关（P〈0.05,n=6）;b与Fe-ox含量呈显著负相关（P〈0.05,n=6）。     

冻融作用对棕壤磷素吸附-解吸特性的影响

以棕壤为研究对象,采用室内模拟冻融环境的方法,研究土壤磷素吸附-解吸行为,采用Langumuir、Freundlich和Temkin方程对吸附过程进行拟合分析,定量研究冻融作用对土壤磷素吸附机制的影响,同时建立土壤磷素解吸量与吸附量关系方程,进一步探讨冻融土壤磷吸附-解吸特性。结果表明,冻融条件下棕壤对磷的吸附规律一致,吸附量均随着平衡溶液中磷浓度增加而逐渐增大,与未冻融土壤相比,冻融后土壤磷等温吸附曲线变得平缓。冻融条件下磷等温吸附曲线用Langmuir方程拟合相关性最好。土壤磷素解吸量与相应最大吸附量符合线性相关。冻融后土壤磷固定吸附量低于未冻融土壤,即冻融过程促进土壤磷素释放,增加了土壤磷流失风险。多次冻融循环对土壤磷吸附-解吸行为影响更为强烈。     

柠檬酸存在下施硅对土壤磷吸附和解吸特性影响

以棕壤为研究对象,采用室内培养的方法,通过加硅酸钙处理、硅酸钙+1 mmol/L柠檬酸处理和硅酸钙+2 mmol/L柠檬酸处理,研究了柠檬酸存在下施硅对棕壤中磷素吸附和解吸特性的影响,并用Langmuir方程、Freundlieh方程与Temkin方程对其进行拟合分析,其中磷吸附解吸试验采用恒温批处理平衡法.结果表明,Langmuir与Temkin模型对处理后棕壤磷的吸附拟合效果最好.硅酸钙+1 mmol/L柠檬酸处理的棕壤对磷的吸附量最大,为500mg/kg;硅酸钙+2 mmol/L柠檬酸处理的棕壤对磷的解吸量及解吸率最大,最大解吸率可达45.2％.因此,硅酸钙+1 mmol/L柠檬酸处理的棕壤对磷肥的储存能力最强,硅酸钙+2 mmol/L柠檬酸处理的棕壤对磷活化能力最强,即供磷能力最强.     

边坡生态防护工程生境基材的磷素吸附-解吸特征

[目的]明确边坡生态防护工程生境基材的磷素保持能力,为优化基材配方提供依据。[方法]以向家坝水电站边坡生态防护工程生境基材为对象,采用恒温振荡培养法进行吸附和解吸试验,比较不同基材的磷素吸附和解吸能力,并用因子分析法比较基材磷素的流失风险。[结果]最大吸附量(Q_m)、最大缓冲容量(MBC)和磷吸持指数(PSI)3个指标均显示,5种基材的固磷能力为:天然次生林客土喷播厚层基材框格梁覆土植被混凝土,Q_m与基材的黏粒含量显著正相关,与有机质含量和pH值显著负相关;磷的解吸能力为:植被混凝土框格梁覆土客土喷播厚层基材天然次生林,平均解吸率与pH值极显著正相关,与有机质含量显著正相关,与黏粒含量显著负相关;因子分析表明Q_m,MBC,PSI、平均解吸率和易解吸磷5个指标可以表示边坡磷素的流失风险。边坡磷素流失风险的大小为:植被混凝土框格梁覆土客土喷播厚层基材天然次生林。[结论]5种生态防护方式中,天然次生林对磷的保持能力最好,植被混凝土基材对磷的保持能力最差;在施工中应当增大基材中黏粒的比重,并适当减少水泥用量或加入缓冲物质,以使基材能够具有较强的磷吸附能力、较大的磷库容和较小的磷流失风险,从而提高磷素的利用率并使其具有持久的供磷能力。     

五种填料对磷酸盐的等温吸附-解吸特性

研究了5种土地处理系统中的常用填料(天然沸石、陶粒、北京土壤、蛭石和砾石)对磷酸盐的吸附和解吸特征,结果表明蛭石与土壤对磷酸盐的吸附效果明显(吸附量分别为1.38 mg/g和1.24 mg/g),陶粒与沸石的磷酸盐吸附效果次之(分别为1.12 mg/g和1.18 mg/g),砾石的磷酸盐吸附效果最差(0.9 mg/g).5种填料在振荡12 h均达到吸附平衡,吸附量随初始磷浓度的增加而增加.砾石的解吸率最高,北京土壤与沸石的次之,蛭石与陶粒的最低.在所研究的五种填料中,从磷吸附量和解吸率来看,蛭石是较好的磷吸附填料.     

长期不同施肥对黄壤磷素吸附–解吸特性的影响

[目的]磷吸附–解吸特性对土壤磷素有效性和环境流失风险有重要影响.研究长期不同施肥对黄壤旱地磷吸附–解吸特性的影响,可为黄壤区合理施用磷肥提供理论依据.[方法]供试黄壤肥力长期定位试验位于贵阳,始于1995年.设有对照(CK)、施氮钾肥(NK)、施氮磷钾肥(NPK)、单施有机肥(M)和有机肥化肥配施(MNPK)5个处理...     

铜尾矿对水溶液中磷的吸附与解吸

为研究铜尾矿作为吸附剂对水溶液中磷的吸附与解吸,从铜陵尾矿库采取尾矿样本,以其作为吸附材料对KH2PO4配制的水溶液进行吸附,用比色法测定磷的平衡浓度,然后计算平衡吸附量和解吸量。结果表明,Langmuir和Freundlich等温吸附方程能够较好地描述铜尾矿对水溶液中磷的吸附过程;尾矿废弃物对水溶液中磷酸根的吸附量与尾矿样本中游离氧化铁、晶质氧化铁、有机络合铁含量以及烧失量呈极显著正相关,而与pH呈极显著负相关;各种植物群落下A层尾矿对磷的吸附量低于C层,尾矿对水溶液中磷的平均最大吸附量超过0.85 mg.g-1,铜官山老尾矿库白茅群落下硬盘层对水溶液中磷的平均最大吸附量达到8.66 mg.g-1,被铜尾矿吸附的磷的平均解吸率低于5%。     

Chemical Characterization of Inorganic Phosphorus Desorbed by Ion Exchange Membranes in Short‐ and Long‐Term Extraction Periods

Abstract

The chemical characterization of soil phosphorus (P) desorbed by anion and cation exchange membranes is of major importance to better understand which P forms are available to plants in short‐ and long‐term time periods. Two distinct soils, one acidic and one calcareous, were analyzed for P using two extraction procedures with mixed anion and cation exchange membranes. The short‐term (ST) experiment evaluated the effect of increasing the extraction periods up to 24 h, whereas the long‐term (LT) experiment consisted of a sequential extraction procedure using up to seven successive 24‐h extractions. In both experiments, the Chang and Jackson inorganic P fractionation methodology was carried out after each extraction treatment, and each treatment consisted of three replicates. Data were statistically analyzed by ANOVA and nonlinear regressions. In the ST experiment, increasing the extraction time increased the extracted P according to an asymptotic relationship (y=c?ab ^x ). Extracted P proceeded from the most labile fractions in the acidic soil. In calcareous soils, calcium phosphates may also contribute for extractable P. The LT experiment revealed that a single extraction, regardless of that extraction method, cannot predict the long‐term capacity of soils to supply P to the plants. An exponential relationship (P=a×n ^b ) was found between extracted P and the extraction number. Desorbed P proceeded from the most labile fractions in the acidic soil. However, in calcareous soils, some precaution is needed when considering the biological meaning of the results, because the occluded Fe phosphates also revealed significant decreases, probably due to the redox conditions in which these long extractions are performed.     

Studies on the maturing process of newly reclaimed soils under cultivation (Part 5) Change of the methoxyl content and the heat of combustion of soil humus under cultivation

It has been considered by investigators, no matter whether they stand by the lignin-protein complex theory or not, that lignin plays an important role in the humus formation of plant residues. When plant residues are added to the soil, though almost all the plant constituents are decomposed, only lignin accumulates in the soil as a component of humus, as it is resistant to the microbial decomposition. However, lignin does not remain unchanged in this case and is thought to be modified, either through chemical agencies or as a result of specific microbial action. Though it is not yet fully clarified what changes it undergoes in the humification process, at least it is indicated that the methoxyl, as a characteristic radical of lignin, is attacked during the process.     

紫色水稻土的有机金属-矿物胶体复合物对磷的吸附、解吸特征

The kinetic characteristics of P adsorption and desorption by organo-mineral colloidal complexes (OMC) were studied using acid, calcareous and neutral purple paddy soils taken from Chongqing and Sichuan, China. The results showed that the P adsorption capacity of the organo-mineral colloidal complexes differed with the soil tyes, being higher for the acid and calcareous purple soils than for the neutral purple soils. Partial removal of the organic matter increased the adsorption capacity of the colloidal complexes. A very significant positive correlation was found between the amounts of P desorbed from OMC and the P saturation degrees. The P adsorption reaction was quick at the early stage and slowed later. The raise of temperature increased P adsorption capacity and P adsorption rate of the colloidal complexes. The adsorption processes could be described by the Elovich equation.     

Wastewater Chemistry and Fractionation of Bioactive Phosphorus in Dairy Manure

Abstract

Because manure organic phosphorus (P) is environmentally bioactive, a novel in situ enzyme hydrolysis assay was developed to identify water soluble‐ and labile complexed P and mechanisms controlling P solubilization in dairy manure. Water‐extractable P averaged 16% (±14.8%) of total P of 107 manures collected across five northeastern states of the USA. Adding a multidentate ligand solubilized inorganic complexed P (15±8.3%) primarily associated with calcium (Ca) and magnesium (Mg). An additional organic fraction (35.9±15.6%) was hydrolyzable by fungal phytases. The assay was more revealing about on‐farm P management than just knowing total P; the water‐extractable P distribution was skewed to the left, and two thirds were <2500 mg kg^?1; bioactive and total P were normally distributed, differing extensively between farms with a range spanning an order of magnitude. The assay's simplicity and robustness over the wide range of manure characteristics may increase routine evaluation of whole‐farm accumulation of environmentally sensitive P forms.     

On the mechanism of specific phosphate adsorption by hydroxylated mineral surfaces: A review

Abstract

The mechanism of specific phosphate adsorption by hydroxy‐lated mineral surfaces comprises two aspects: the phosphate‐hydroxyl surface reaction and the configuration of the adsorbed phosphate ion. Evidence pointing to ligand exchange as the mechanism of the phosphate‐surface hydroxyl reaction include kinetics of adsorption and desorption; hydroxyl ion release; infrared spectroscopy, and stereochemical calculations. Data pertaining to the coordination of adsorbed phosphate on hydroxy‐lated mineral surfaces have not been conclusive overall. Isotopic exchange experiments and studies of desorption kinetics do not provide definitive information on surface coordination. Measurements of hydroxyl ion release and crystallographic calculations provide support for the existence of both monodentate and bidentate surface complexes of phosphate ions. Infrared spectroscopic investigations suggest a binuclear complex on dried, phosphated goethite. However, these studies cannot be extrapolated automatically to soil minerals, since the addition of water favors formation of a monodentate surface complex. Further research is needed to establish the configuration of adsorbed phosphate ions.     

Long-term effects of bone char and lignocellulosic biochar-based soil amendments on phosphorus adsorption–desorption and crop yield in low-input acidic soils

Although the addition of biochar has been shown to reduce the phosphorus (P) adsorption capacity of soil, quantitative evidence of this has mainly been provided by incubation experiments and it is therefore essential to conduct long-term field trials to draw general conclusions. It is largely unknown whether bone char has a greater effect than lignocellulosic biochar on P adsorption–desorption processes and crop yield. The aim of this study was to determine the long-term (8 years) effect of bone char and biochar on P adsorption–desorption and crop yield in low-input acidic soils. The results showed that bone char decreased the maximum P adsorption capacity (Q_m) by 10% and increased the desorption capacity (D_s) by 150% compared with the control (i.e. without a soil amendment). The desorption ratio was highest for the bone char treatment (10.3%) and three times more than the control. Plant-available P was seven times greater under bone char than the control. There was no variation in adsorption–desorption characteristics, desorption ratio and plant-P available content between bone char and lignocellulosic biochar treatments. The average yield increment following the application of bone char and biochar was 1.7 and 1.4 Mg ha⁻¹ for maize and 1.8 and 1.9 Mg ha⁻¹ for soya bean, respectively. Despite the low application rate (4 t ha⁻¹ year⁻¹), these findings demonstrated that the long-term application of bone char and biochar-based amendments enhanced P availability in low-input cropping systems, mainly by altering the P adsorption and desorption capacity of soils.