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。     

Adsorption of phthalic acid and salicylic acid by two variable charge soils as influenced by sulphate and phosphate

Low‐molecular‐weight (LMW) organic acids exist widely in soils, especially in the rhizosphere, and the adsorption of these acids may affect their reactions in soils. The adsorption behaviour of phthalic acid and salicylic acid by two variable charge soils (a Rhodic Ferralsol and a Haplic Acrisol) was investigated. Both soils exhibited great adsorption capacity for these organic acids, with a greater affinity for phthalic acid. The Rhodic Ferralsol adsorbed more organic acids of both kinds than the Haplic Acrisol, which was consistent with the content of iron and aluminum oxides in the two soils. The iron oxides in these soils played a significant role in adsorption of the organic acids, whilst the soil aluminosilicate minerals, such as kaolinite, showed a small adsorption capacity. The presence of phosphate and sulphate caused a decrease in the adsorption of both organic acids because of their competition with them for sorption sites. The phosphate showed a bigger inhibition on the adsorption than sulphate as a result of a greater amount of phosphate adsorbed by the soils. The adsorption of both organic acids was affected by pH only slightly at pH < 4.5. However, the adsorption decreased with the increase in pH at pH > 4.5. A similar trend was observed for the phosphate system, but the opposite was seen for the sulphate system. This suggests that the inhibition of sulphate on the adsorption of the organic acids decreased with the increase in pH, because the adsorption of sulphate decreased strongly with increasing pH.     

除草剂草甘膦在几种土壤和矿物上的吸附研究

通过批平衡实验考察了草甘膦在几种性质不同土壤和矿物上的吸附行为。研究发现土壤对草甘膦有较强的吸附能力，草甘膦在土壤上吸附量的大小与土壤理化性质密切相关。草甘膦在土壤和矿物上的吸附符合Freundlich吸附方程，其在土壤上的吸附常数K与土壤粘粒含量呈正相关，并随土壤氧化铁和氧化铝含量增加而增加，而与土壤的pH呈显著负相关。草甘膦在高岭石上的吸附量要比在蒙脱石上大，而草甘膦在金属离子饱和的蒙脱石和高岭石上的吸附研究结果表明，草甘膦在钠、钙、铁离子饱和的矿物上的吸附能力依次为Fe-蒙脱石〉Ca-蒙脱石〉Na-蒙脱石和Fe-高岭石〉Ca-高岭石〉Na-高岭石。     

支持电解质浓度对磷酸根在可变电荷土壤表面吸附和解吸的影响

研究了离子强度对2种可变电荷土壤中磷酸根吸附和解吸的影响。结果表明,当pH分别大于3.7和4.0时,红壤和砖红壤对磷酸根的吸附量随离子强度的增加而增加;当pH分别小于3.7和4.0时,红壤和砖红壤对磷酸根的吸附量随离子强度呈相反的变化趋势。电解质主要通过改变离子专性吸附面上的电位来影响磷酸根的吸附。Zeta电位的测定结果表明,当pH大于土壤胶体的等电点(IEP)时,吸附面上电位为负值,且随离子强度增加数值减小,对磷酸根的排斥力减小,土壤表面对磷酸根的吸附量增加;当pH小于IEP时,吸附面上的电位为正值,它随离子强度增加而减小,不利于磷酸根的吸附。解吸实验的结果表明,吸附于可变电荷土壤表面的磷酸根在去离子水中的解吸量高于0.1 mol L-1NaNO3体系中的解吸量。这同样由于电解质浓度对土壤表面吸附面上的电位的影响所致。     

Reactions of nucleic acid bases with inorganic soil constituents

The adsorption at pH's 4, 6 and 8 of adenine, guanine, cytosine, thymine and uracil on clays (montmorillonite, illite and kaolinite), Fe- and Al-oxides (goethite, hematite and gibbsite), a soil, and on a laboratory-prepared fulvic acid-montmorillonite complex was investigated. Portions of the clays and soil were saturated with H⁺, Fe³⁺ and Ca²⁺.Quantitatively, the extent of adsorption of nucleic acid bases by the clays was proportional to their exchange capacities, but the nature of the dominant cation had only minor effects. By contrast, the adsorption was strongly affected by pH, tending to decrease with increase in pH. Adsorption on goethite and gibbsite was lower than that on clays, while adsorption of nucleic acid bases on soils was slightly lower than that on oxides. The fulvic acid-montmorillonite complex adsorbed substantial, although smaller amounts of purines and pyrimidines, than did montmorillonite alone. The main adsorption mechanism at pH 4 appeared to be cation exchange whereas at pH 8 complex formation between the nucleic acid bases and cations on inorganic surfaces seemed to occur.The results of this and earlier work show that both inorganic and organic soil constituents adsorb nucleic acid bases. Which adsorption reaction predominates will depend on the clay and organic matter content and on the pH.     

磷矿粉在酸性土壤中的施用: 比较磷酸盐提取方法测定磷矿粉溶解程度

Three phosphate extraction methods were used to investigate the dissolution,availability and transfo-mation of Kunyang phosphate rock(KPR) in two surface acid soils.Dissolution was determined by measuring the increase in the amounts of soluble and adsorbed inorganic phosphate fractions,and did not differ signifi-cantly among the three methods.Significant correlations were obtained among P fractions got by the three extraction methods.Dissolution continued until the end of the 90-day incubation period.At the end of the period,much of the applied phosphate recovered in both soils were in the Al- and Fe-P or in the hydroxide-and bicarbonate-extractable inorganic P fractions.The dissolution of KPR in the two soils was also similar: increased addition of phosphate rock resulted in decreased dissolution.The similarity in the order and extent of dissolution in the two soils was probably due to the similarity in each soil of several factors that are known to influence phosphate rock dissolution,namely low CEC,pH,P level,and base status;and high clay and free iron and aluminum oxide contents.The results suggested that KPR could be an aternative P source in the soils are not limiting.     

亚热带土壤不同矿物组分中铬的吸附

Safe application of chromium (Cr)-containing organic industrial wastes to soil requires considering the ability of the soil to adsorb Cr.In this study,the maximum Cr adsorption capacity was assessed for the bulk samples and their clay and iron-free clay fractions of four subtropical soils differing in mineralogy.To this end,the samples were supplied with Cr(Ⅲ) nitrate solutions at pH 4.5 or 5.5.The results of Cr(Ⅲ) adsorption fitted to a Freundlich equation and the adsorption capacity was positively correlated with soil organic matter and iron oxide contents.The clay fractions adsorbed more Cr per unit mass than the bulk soils and the iron-free clay fractions.The Cr(Ⅲ) adsorption capacity increased with increasing soil pH due to more charges on adsorbing surfaces.Our results suggest that the soils rich in organic matter and iron oxides and having a pH above 4.5 are suitable for application of Cr(Ⅲ)-loaded industrial wastes.     

SPECIFIC ADSORPTION OF SILICATE AND PHOSPHATE BY SOILS

The adsorption of silicate and phosphate from pure and mixed solutions by four soils known to fix phosphate strongly has been measured. The adsorption at constant pH for each acid from its pure solution follows the Langmuir isotherm. The maximum adsorption of silicate by three of the soils from the pure solution occurs at pH 9.2, and the maximum adsorption curve for phosphate by two of the soils from its pure solution has a break in its slope at pH 6.4 and 11.6. These pHs are all just below the pK values for the dissociation of hydrogen ions from the undissociated silicic acid or the acid phosphate anions. The presence of silicate in a mixed solution, which is sufficiently concentrated in both silicate and phosphate to give maximum adsorption of either if in pure solution, does not affect the amount of phosphate adsorbed until the pH is over 6.5–7.0. At this pH the maximum adsorption curve for silicate crosses that for phosphate. The presence of phosphate in the mixed solution always depresses the adsorption of silicate. The maximum amount of silicate-plus-phosphate adsorbed from this mixed solution is either a little less than or equal to the amount of silicate adsorbed from the pure silicate solution if the pH is above 7. When silicate displaces phosphate, or phosphate displaces silicate, more moles of the displacing acid are adsorbed than moles of the displaced acid released. These results for soils are similar to those of Hingston et al. for the adsorption of silicate and phosphate by goethite.     

Phosphorus adsorption by surface samples of five ironpan soils of Ghana

Phosphorus adsorption by surface samples of five ironpan soils (Kumayili, Kpelesawgu, Nyankpala, Wenchi and Changnalili series) within the Guinea Savannah zone of Ghana were studied. The samples differed in their capacity to adsorb added inorganic P. Per cent adsorbed P decreased as P additions and equilibrium P concentrations increased. P adsorption isotherms obtained were in two parts, and approximately 25 and 40% of the total adsorption was represented by the first lower part of the Langmuir isotherm. Phosphorus adsorbed correlated with percentage organic matter, oxalate-extractable Al and dithionite-HCl-extractable Fe but not with percentage clay, pH and dithionite-citrate-extractable Fe. Fractionation following six days of equilibration showed that added inorganic P was retained mostly as Al-P rather than as Fe-P. It was found that samples of three of the ironpan soils, the Kumayili, ?Kpelesawgu and Nyankpala series, have low P adsorption capacities.     

Competitive adsorption of humus acids and phosphate on goethite, gibbsite and two tropical soils

Competition in adsorption between humic acid (HA) or fulvic acid (FA) and phosphate on synthetic goethite, gibbsite and two tropical soils was studied. The results for both goethite and gibbsite showed that HA and FA competed strongly with phosphate for adsorption sites at low pH values. The soils showed a similar result with a reduction in phosphate adsorption resulting from the addition of HA at the pH of the soils. The competition between HA and phosphate at different pH levels is illustrated by comparing the adsorption envelopes for phosphate on goethite, gibbsite and the two soils in the presence and absence of HA. The trends observed may be explained by the relative positions of the maximum buffer-power (buffer capacity) of the organic acids and of phosphoric acid which are shown to lie in different pH ranges.     

可溶性有机碳在典型土壤上的吸附行为及机理

定量分析可溶性有机碳(DOC)在不同土壤上的吸附行为可为DOC在不同地区土壤中的去向及污染风险评估提供理论基础。本研究以河南潮土(包括砂质、壤质和黏质3种质地)、江苏黄泥土、江西红黏土和海南砖红壤等典型土壤为吸附介质,采用一次平衡法比较了DOC在不同土壤中的吸附容量及平衡液中DOC的结构变化。结果表明,供试土壤对DOC的吸附可用修正的Langmuir模型拟合。最大吸附量(Q_(max))从高到低依次为红黏土(2 892.67 mg/kg)、砖红壤(1 969.77 mg/kg)、黏质潮土(1 803.03 mg/kg)、黄泥土(1 003.84 mg/kg)、壤质潮土(989.31 mg/kg)和砂质潮土(441.18 mg/kg)。黄泥土的亲和系数(k)最大(2.53×10~(–3)),其次为砖红壤、红黏土和3种潮土。吸附后,除砂质潮土和壤质潮土外,其他土壤平衡液的芳香性均降低。相关性分析表明无定形氧化铝显著影响了Q_(max),而氧化铁的形态(无定形、络合态和低结晶态)决定了k值大小。红黏土、砖红壤和黄泥土更容易吸附DOC中的芳香族成分,主要吸附机制可能为配位体交换;砂质潮土和壤质潮土主要为阳离子架桥,而黏质潮土同时存在这两种吸附机制。     

Adsorption of DNA on clay minerals and various colloidal particles from an Alfisol

Adsorption and desorption of salmon sperm DNA on four different colloidal fractions from Brown Soil and clay minerals were studied. The adsorption isotherms of DNA on the examined soil colloids and minerals conformed to the Langmuir equation. The amount of DNA adsorbed followed the order: montmorillonite?fine inorganic clay>fine organic clay>kaolinite>coarse inorganic clay>coarse organic clay. A marked decrease in the adsorption of DNA on organic clays and montmorillonite was observed with the increase of pH from 2.0 to 5.0. Negligible DNA was adsorbed by organic clays above pH 5.0. As for inorganic clays and kaolinite, a slow decrease in DNA adsorption was found with increasing pH from 2.0 to 9.0. The results implied that electrostatic interactions played a more important role in DNA adsorption on organic clays and montmorillonite. Magnesium ion was more efficient than sodium ion in promoting DNA adsorption on soil colloids and minerals. DNA molecules on soil colloids and minerals were desorbed by sequential washing with 10 mM Tris, 100 mM NaCl and 100 mM phosphate at pH 7.0. A percentage of 53.7-64.4% of adsorbed DNA on organic clays and montmorillonite was released, while only 10.7-15.2% of DNA on inorganic clays and kaolinite was desorbed by Tris and NaCl. The percent desorption of DNA from inorganic clays, organic clays, montmorillonite and kaolinite by phosphate was 39.7-42.2, 23.6-28.8, 29.7 and 11.4%, respectively. Data from this work indicated that fine clays dominate the amount of DNA adsorption and coarse clays play a more important role in the binding affinity of DNA in soil. Organic matter may not favor DNA adsorption in permanent-charge soil. The information obtained is of fundamental significance for the understanding of the ultimate fate of extracellular DNA in soil.     

Effect of iron oxide removal on heavy metal sorption by acid subsoils

The adsorption of Cd, Cu, Pb, and Zn from 0.025 M NaClO₄ solutions by two ferruginous subsoils, Christiana silty clay loam and Dothan sandy clay, was investigated. Under acidic conditions, selective dissolution and removal of the Fe oxide soil component by dithionite-citrate-bicarbonate (DCB) generally increased heavy metal adsorption by the soils. This effect was attributed to increased electrostatic attraction of cations to the DCB-washed soils as evidenced by substantial reduction in the zero point of charge (ZPC) for the Dothan soil following DCB extraction. Alternately, the DCB extraction stripped Fe and Al species bound to structural exchange sites or eliminated coatings which reduce cation accessibility to such sites. Addition of low levels (10^?6 M) of ferric iron suppressed heavy metal adsorption capacity of the DCB-extracted Christiana soil to values comparable to the unmodified whole soil system. While hydrous oxide surfaces represent highly reactive sites for cation binding, Fe oxides can modify both the pH-dependent and structural exchange sites in a manner which hinders heavy metal adsorption. Thus, a soil's Fe-oxide content is unlikely to be a reliable guide to heavy metal adsorption capacity.     

在MAF和DAP体系中土壤锌吸附的初步研究

本文研究了MAP和DAP对黄土土壤吸附锌的影响及生物效果。结果表明,MAP和DAP磷酸盐可以引起土壤平衡锌溶液pH的变化,从而影响着土壤吸附锌的模式。MAP减弱土壤的吸锌量;相反,DAP降低了锌的活性,增加了固锌量。这种影响对有机质和粘粒含量低的土壤尤为显著。生物试验结果表明,MAP不仅能促进植株对锌的吸收,而且,锌-磷交互效应显著;相反,DAP却减少了锌的吸收。锌-磷交互效应低。     

Glyphosate adsorption on synthetic allophanes and halloysite: Effects of pH and mineral properties

Background

Glyphosate (GLP) is a widely used herbicide with possible adverse effects on human health and the environment. In soils, GLP strongly adsorbs on clay-sized minerals, depending on pH, the amount of organic carbon, as well as the contents and properties of Al and Fe oxyhydroxides and clay minerals. Many clay-sized minerals have already been investigated regarding GLP adsorption behavior, but information on minerals commonly found in volcanic soils is still lacking.

Aim

The aim of this study was to investigate for the first time the pH-dependent adsorption of GLP on allophane and halloysite, typical minerals found in volcanic soils.

Methods

GLP adsorption was studied in batch experiments at three pH values (5, 6, and 7). Synthetic allophanes with two different initial Al:Si ratios (1.4 and 1.8) and a halloysite were used as adsorbents.

Results

The adsorption capacity (AC) increased with rising Al:Si ratio and decreasing pH. The AC of allophane was significantly higher than that of halloysite. GLP adsorption on allophane was larger than that reported for other clay minerals and Al and Fe oxyhydroxides, especially at low pH. The AC of halloysite was higher than reported for most other clay minerals.

Conclusion

Different mineral formation pathways in volcanic soils, notably the formation of halloysite versus allophanes, strongly affect the soils’ retention capacity for GLP. The high AC of allophanes may induce the low mobility of GLP in allophane-containing soils. Long-term use of GLP may accumulate the herbicide in these soils with potential effects on biodiversity and ecosystem services.     

上海土壤磷的吸附特性及缓冲性能的研究

本文以上海土壤为对象,研究选定了土壤磷等温吸附试验条件为:水土比10,平衡时间6天,控温25℃,磷加入量为100,200,400,600μgP/g土,溶液基质为0.01M CaCl₂。磷缓冲能力试验条件为:平衡时间2天,磷加入量为20,40,100,200μgP/g土。根据Freundlich, Tempkin和Langmuir方程计算的土壤吸附指标与土壤类型及土壤性质有密切关系,是土壤磷素肥力的重要指标。反映土壤缓冲能力的“磷肥指标”与土壤有机质、粘粒、活性铝及pH值相关较好。上海几种主要土壤中以青紫泥的最大吸附量(X_m),0.2ppm P吸附量和“磷肥指标”为最高,其次为青黄土,沟干泥和黄泥头,最小为夹沙泥。应用磷吸附指标与“磷肥指标”来预测土壤需磷量,初步试验是可行的,但实际应用还需进一步试验研究。     

农药草甘膦在砂质潮土上的迁移行为及其影响因素

化学物质在土壤中的移动性是人们精确评价其潜在淋溶能力(即对地下水的污染风险)的必要信息。通过一次平衡法和饱和土柱稳定流混合置换实验,来阐明环境pH变化和磷酸盐施用对草甘膦在砂质潮土中的吸附和迁移行为的影响。结果表明,草甘膦在砂质潮土上的吸附量随着pH的增大而降低,在pH4~6的范围内吸附量变化最明显;其穿透曲线(BTCs)均呈现不同程度的不对称性,加入的草甘膦浓度越低这种不对称性越明显;在本实验条件下,施用磷酸盐有抑制草甘膦迁移的趋势,但其抑制趋势并非随磷酸盐施用量的增加而持续增加。如加入草甘膦浓度为500 mg L-1,不加磷酸盐P0时,流出液中草甘膦峰值为459.8mg L-1,而加入磷酸盐P1和P2时,其峰值分别为147.3 mg L-1和373.6 mg L-1。推测其原因可能与磷酸盐施用导致环境pH降低及磷酸盐在加草甘膦前已经占据过多的吸附位点有关。     

Phosphate sorption by red mediterranean soils from Greece

Abstract

In nineteen surface horizons of red Mediterranean soils from various locations of Greece, phosphorus (P) sorption experiments were conducted and the sorption characteristics were studied in relation to soil properties. Phosphate sorption data were fitted both to the Langmuir and Freundlich equations. From these equations, the following P sorption parameters were determined from the Freundlich equation, X = ACⁿ, the parameters A (the phosphate sorbed at C = 1 mg P/L), n (the P sorption intensity), the P sorption index (PS = X/log C) and maximum P sorption (Xmfr). From the Langmuir equation, C/X = 1/KXm + C/Xm, the parameters K (showing the bonding energy), maximum P sorption (Xmla), the quantity of P adsorbed at a standard concentration of 0.2 mg P/L (P0.2), and P maximum buffering capacity (PMBC). The Freundlich parameter A was strongly correlated to the clay and sesquioxides ("free”; iron and aluminum oxides and amorphous iron oxides) content. Seventy‐four percent of the variance of this parameter was explained by clay and “free”; iron (Fe) content. The Freundlich parameter n was significantly correlated with pH and amorphous iron oxides content, while 52% of its variance was explained by amorphous Fe and dithionite extrac‐table aluminum (Al). The P sorption maxima calculated from the Freundlich equation were in general lower than those calculated by the Langmuir equation. Both these parameters were strongly correlated with clay and more slightly with sesquioxides content. About 50% of their variance was explained by clay content of the soils. The P sorption index was strongly correlated with the clay content and less strongly with dithionite‐extractable Fe and Al. The P‐buffering capacity calculated from the data of Langmuir equation was also strongly correlated with these two parameters. In addition, clay content and dithionite‐extractable Fe and Al were well correlated to the amounts of P required to obtain an equilibrium concentration of 0.2 mg P/L while 61% of the variation of this parameter was explained by the clay and the dithionite‐extractable Fe content. From these findings, it seems that for the red Mediterranean soils from Greece, P sorption is affected by clay content and iron and aluminum oxide contents.     

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。     

Effect of Low Molecular Weight Organic Anions on Adsorption of Aluminum by Variable Charge Soils

To examine the effect of organic anions on adsorption of Al by variable charge soils at different pH values, the adsorption by three soils in the presence of three low-molecular-weight aliphatic carboxylic acids was investigated. The results showed that the effect depended on pH, the type of organic anions and their concentration. The presence of citrate and oxalate led to an increase in the adsorption of Al at low pH and low concentration of organic anions, with citrate showing a stronger effect than oxalate. For example, the maximum increments of Al adsorption in the presence of citrate were 131.9, 104.8 and 32.9% in the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively, whereas in the presence of oxalate it was 36.1% in the Rhodic Ferralsol. At high pH or high concentration of organic anions, they showed an inhibiting effect on the adsorption of Al. For example, citrate caused the increase in Al adsorption by 164.0, 131.0 and 61.0% at pH3.85 and the decrease in Al adsorption by 15.2, 19.5 and 45.6% at pH 4.8 for the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively. In the citrate and oxalate systems, the adsorption of Al increased with the increase in the concentration of organic anions, reaching a maximum values at about 0.4 mmol L^?1, and then decreased. When the concentration of organic anions was higher than about 1.0 mmol L^?1, both citrate and oxalate inhibited the adsorption of Al. The ability of organic anions in increasing the adsorption at low pH and decreasing the adsorption at high pH followed the same order: citrate > oxalate > acetate. The increase of Al adsorption at low pH is caused by the increase in soil negative surface charge as a result of the adsorption of organic anions by variable charge soils, while the decrease of Al adsorption at high pH and high concentration of organic anions is related to the competition of organic ligands for aluminum ions with soil surface. After the removal of free iron oxides from the soil, Al adsorption decreased in the presence of citrate, the anion species most strongly adsorbed by variable charge soils and complexed with aluminum ions. For example, for the Rhodic Ferralsol and the Ferric Acrisol, the removal of free iron oxides caused a decrease in the adsorption of Al in the presence of citrate at pH4.4 by 26.2 and 21.9%, respectively.