Adsorption and Transformation Reactions of L-DOPA in Soils

3-(3′,4′-Dihydroxyphenyl)-L-alanine (L-DOPA), which is a component of velvetbean (Mucuna pruriens), displays a high inhibitory activity to plant growth. The inhibitory activity is influenced by the presence of soils, because L-DOPA is eliminated in soils. In the present study, the effect of several soil types (volcanic ash, calcareous, and alluvial soils) on the L-DOPA disappearance was investigated at constant equilibrium pH values. In the presence of soils, L-DOPA disappeared with the reaction time, and the disappearance was associated with three reactions: adsorption reaction (characterized by fast and sudden disappearance of L-DOPA within the initial 8 h period), catalytic transformation reaction (constant L-DOPA disappearance throughout the reaction period), and biotransformation caused by microbial activity (accelerated L-DOPA disappearance observed after 72 h of reaction time). The adsorption and transformation reactions consisted of physicochemical reactions mediated by the presence of soils. The amount of L-DOPA adsorbed was largest in the presence of volcanic ash soil among the three soil types. It is likely that the mechanism of L-DOPA adsorption includes a ligand exchange reaction. In the presence of soils, L-DOPA transformation was observed at equilibrium pH values higher than 4 and it increased with increasing equilibrium pH values. In the absence of soil, however, L-DOPA transformation did not occur at an equilibrium pH value lower than 6.0, indicating that L-DOPA transformation was accelerated by the presence of soil. The rate of L-DOPA transformation mediated by soils at constant equilibrium pH value was in the following order: alluvial soil > calcareous soil > volcanic ash soil. The plant-growth-inhibitory activity of L-DOPA was also reduced by the presence of soils, and the reduction in the case of L-DOPA was more obvious than in the case of 2,4-dichlorophenoxyacetic acid (2,4-D). Based on the reduction effect of soils on the plant-growth-inhibitory activity of L-DOPA (without pH-adjustment), calcareous soil ranked first, followed by volcanic ash soil, then alluvial soil. This was because the calcareous soil showed the highest soil pH value (7.8), and thereby the L-DOPA transformation reaction was accelerated. In soils with high pH values, the plant-growth-inhibitory activity of L-DOPA could therefore not be detected.     

Effect of α-casein on DNA adsorption by Andosols and by soil components

Andosols and the soil components (allophanes, humic acids, and goethite) had been autoclaved to destroy the nuclease activity of soil microflora. DNA adsorption by allophanes and Andosols was decreased by increasing the amount of α-casein added to the allophanes and to soils up to casein concentration of 5 mg ml^?1. DNA adsorption by humic acids was significantly increased by increasing the amount of α-casein up to 1.0 mg ml^?1, whereas the addition of 20 mg α-casein ml^?1 completely blocked DNA adsorption. These results can explain why the addition of excess skim milk is operationally needed for effective DNA extraction from Andosols. The amount of DNA adsorbed by Andosols treated with dephosphorylated α-casein was significantly higher than that of not treated Andosols (p?相似文献   

Influence of Soil Chemical Properties on Adsorption and Oxidation of Phenolic Acids in Soil Suspension

Relationships between abiotic oxidation and adsorption of phenolic acids added to soils and soil chemical properties were investigated by using 32 soil samples and ferulic, vanillic, and p-hydroxybenzoic acids. Soil properties studied were as follows: (as adsorption factors) contents of acid oxalate extractable Al (Alo), Fe (Feo), dithionite-citrate-bicarbonate (DCB) extractable Fe (Fed), total carbon and clay, and (as oxidation factors) level of soil oxidative activity (Cr oxidation) determined by the amount of Cr(VI) converted from Cr(III) added to soils. Soil samples were divided into 3 types based on chemical properties: Andosols A (A horizon of Andosols), Andosols B (B horizon of Andosols and light-colored Andosols), and non-Andosols.

The recovery of all phenolic acids (RPA) was negatively correlated with the total carbon and Feo contents in Andosols A and B, respectively, which suggested adsorption onto soil organic matter in Andosols A and onto Feo in Andosols B. It was considered that almost no oxidation of phenolic acids occurred in Andosols A, because a very small amount of Cr(VI) was obtained. The recovery of ferulic acid (RFA) and vanillic acid (RVA), however, was negatively correlated with Cr oxidation in non-Andosols, suggesting that these phenolic acids were oxidized, while almost all of the p-hydroxybenzoic acid was recovered.

These results were also supported by the comparison between RFA and recovery of dissolved organic carbon (RTOC). RFA was very similar to RTOC in Andosols A and B, which indicated that adsorption occurred, whereas RFA was lower than RTOC in the non-Andosols that showed a high level of Cr oxidation, indicating that oxidation took place. Manganese dissolution which occurred when phenolic acids were added to soils was also examined.     

Adsorption of herbicidally active degradate 2-(2,4-dichloro-3-methylphenoxy)propanoic acid on an andosol

The adsorption of 2-(2,4-dichloro-3-methylphenoxy)propanoic acid (DMPA) on the surface horizon of a humus-rich Andosol was examined. To investigate the mechanisms of adsorption, chemically treated Andosols, such as organic matter removed Andosol, organic matter and active metals removed Andosol, and clay minerals of the Andosol, were prepared. Furthermore, humic acid was extracted from the Andosol. The mechanisms of the DMPA adsorption were identified by using those untreated and chemically treated Andosols and the humic acid. The amount of DMPA adsorbed increased with decreasing equilibrium pH value. Active surface hydroxyl groups were identified as the most important soil functional group in DMPA adsorption. The predominant mechanism of DMPA adsorption on the Andosol is a ligand-exchange reaction, in which an active surface hydroxyl on Al and/or Fe is replaced by a carboxylic group of DMPA. A comparative study revealed that the amount of DMPA adsorbed was slightly greater than that of (2,4-dichlorophenoxy)acetic acid (2,4-D), especially at equilibrium pH values below 5. This is because the octanol-water partition coefficient (log Kow) of DMPA in the equilibrium pH range is higher than that of 2,4-D, and SOM participates in the adsorption process through a hydrophobic interaction.     

Relationships between the High Aluminum Concentration and Other Components in Soil Solution of Acidic Soil in Kumagaya, Central Japan

A plot with a high aluminum (Al) concentration in soil solution was found in Kumagaya, central Japan; the maximum was 4.0 mg L⁻¹ as total dissolved Al (TD-Al) at a depth of 10 cm in August 2000. The soil type was Dystric Andosols with three horizons, A/Bw1/Bw2, which contained a considerable quantity of Al extracted by dithionite-citrate and acid-oxalate extractants. The upper two horizons were acidic with soil pH (H₂O) of 4.4 and 4.6. The fundamental cause of the high TD-Al concentration was the low pH with a very low base saturation of less than 2%. The seasonal change in TD-Al concentrations in soil solution at a depth of 10 cm was significantly and positively correlated with the nitrate concentrations but weakly and rather negatively correlated with the sulfate concentrations. Nitrification functioned as the direct acid source to cause the TD-Al concentrations to fluctuate strongly, whereas sulfate adsorption onto the soil at the research plot functioned as a sink of proton.     

外源铜和镍在土壤中的化学形态及其老化研究

采用连续提取法测定了外源铜和镍进入田间土壤后的化学形态分布,比较研究了这2种重金属在3种不同类型土壤(红壤,水稻土和潮土)中随老化时间的形态转化和分布.结果表明,外源铜以残留态(40%～60%)和EDTA可提取态(40%)为主;随老化时间,EDTA可提取态、易还原锰结合态及铁铝氧化态向残留态转化;外源镍在酸性红壤中以可交换态(40%)和残留态(30%～50%)为主,在中性水稻土中以EDTA可提取态(30%)和残留态(30%～50%)为主,在碱性潮土中以铁铝氧化态(20%)和残留态(40%)为主.随老化时间,水溶态、可交换态、EDTA可提取态等向残留态转化.土壤pH较低时水溶态和可交换态含量较高,但是同时随老化时间的降低量也明显;pH较高时有利于易还原锰结合态和有机质结合态的转化.     

Adsorption—desorption and/or precipitation—dissolution processes of zinc in soils

The concentrations of trace and toxic metals in soil solutions are explained by several authors either in terms of adsorption—desorption or precipitation—dissolution reactions in soils. Data have been given for zinc to test the applicability of both concepts. The results show that the concentrations of zinc in equilibrium solutions with soil clay fractions and whole soil samples at pH values below 7 are determined exclusively by adsorption—desorption reactions for various pH's, contents of bound zinc and compositions of soils. At neutral to alkaline pH values precipitation—dissolution reactions of zinc may take place. There is some evidence that formation of zinc silicates may control the zinc concentration in solution provided natural complexing agents are absent, the affinity of the soil for zinc is low and the content of reaching zinc is high (> ～ 100 ppm). Even at pH values above 7, the formation of other zinc compounds is unlikely in most soils because additions of large amounts of zinc are required to ensure saturation of the adsorption sites of different soil components before the zinc concentration in the soil solution can increase sufficiently to bring about the precipitation of definite compounds. Model experiments in CaCO₃-buffered systems showed that the adsorption capacity for specifically adsorbed zinc (in μmole/g) by the following components increased in the order CaCO₃ (0.44), bentonite (44), humic acid (842), amorphous Fe- and Al-oxides (1190, 1310) and δ -MnO₂ (1540) and demonstrated the importance of Mn-, Fe-, and Al-oxides and humic substances for the binding of zinc in soils containing carbonates, and thus indicate the special role of these components in limiting precipitation reactions.     

Radiocesium transfer from Andosols to brown rice in the northern and northwest areas of Tochigi Prefecture,in the first 3 years following the 2011 Fukushima Daiichi nuclear power plant accident

ABSTRACT

Following the Fukushima Daiichi Nuclear Power Plant accident of 2011, the potential for radiocesium transfer from contaminated soils, such as Andosols, to agricultural crops became a significant concern. Andosols account for up to 70％ of paddy soils in the northern and northwest areas of Tochigi Prefecture, where the radiocesium concentration is 1000 Bq kg^?1 or greater in the soil of some fields. The present study was carried out in order to determine the phytoavailability of radiocesium in Andosols by comparing it with that of gray lowland soils in the first 3 years following the accident. The transfer factor (TF) tended to be higher in Andosols than in gray lowland soils, leading to higher radiocesium concentrations in brown rice grown in Andosols. The exchangeable potassium (Ex-K₂O) in Andosols was highly and negatively correlated with TF, followed by clay. The Ex-K₂O value was positively correlated with the clay/total carbon (T-C) value, suggesting that a high T–C ratio could weaken K₂O adsorption on clay mineral sites; hence, the low clay/T-C values can partially explain the relatively large TF values of Andosols. Samples with Ex-K₂O contents less than 200 mg kg^?1 and with low clay/T-C values showed striking decreases in TF values from 2011 to 2012. However, the decrease from 2012 to 2013 was quite small; radiocesium in these samples was potentially available for rice uptake for a long time, likely due to the reversible adsorption and fixation characteristics of allophane. Most gray lowland soil samples showed very low TF values over the 3 years of the study, except for those with TF values greater than 0.1 due to low Ex-K₂O and clay contents; the geometric mean (GM) value of TF was below 0.01 in 2012. The extraction of exchangeable radiocesium (Ex-Cs) with a 1 mol L^?1 ammonium acetate solution may not be an appropriate method for explaining the variability in radiocesium TF in Andosols. This is because the Ex-Cs value was significantly correlated with Ex-K₂O in Andosols, but not in gray lowland soils, indicating that Ex-K₂O explained this variability in relation to Ex-Cs.     

四种土壤调理剂对镉、铅的吸附效果研究

采用等温吸附试验研究了主要原料为麦饭石(M)、蒙脱石(T)、牡蛎壳(O)和硅钙矿(S)4种土壤调理剂对溶液中镉和铅的吸附效果。结果表明,4种土壤调理剂对镉和铅的吸附均可用Langmuir方程进行描述;相比而言,4种土壤调理剂对镉吸附量的大小顺序为O调理剂>S调理剂>M调理剂>T调理剂,对铅吸附量的大小顺序为M调理剂>S调理剂>O调理剂>T调理剂;随溶液pH值的增大各调理剂的吸附量逐渐减小,尤其当Cd溶液pH值>8,Pb溶液pH值>6,各调理剂的吸附量迅速降低。     

Adsorption and Desorption of Copper in Pasture Soils

Abstract

Copper (Cu) is bound strongly to organic matter, oxides of iron (Fe) and manganese (Mn), and clay minerals in soils. To investigate the relative contribution of different soil components in the sorption of Cu, sorption was measured after the removal of various other soil components; organic matter and aluminum (Al) and Fe oxides are important in Cu adsorption. Both adsorption and desorption of Cu at various pH values were also measured by using diverse pasture soils. The differences in the sorption of Cu between the soils are attributed to the differences in the chemical characteristics of the soils. Copper sorption, as measured by the Freundlich equation sorption constants [potassium (K) and nitrogen (N)], was strongly correlated with soil properties, such as silt content, organic carbon, and soil pH. The relative importance of organic matter and oxides on Cu adsorption decreased and increased, respectively, with increasing solution Cu concentrations. In all soils, Cu sorption increased with increasing pH, but the solution Cu concentration decreased with increasing soil pH. The cumulative amounts of native and added soil Cu desorbed from two contrasting soils (Manawatu and Ngamoka) during desorption periods showed that the differences in the desorbability of Cu were a result of differences in the physico‐chemical properties of the soil matrix. This finding suggests that soil organic matter complexes of Cu added through fertilizer, resulted in decreased desorption. The proportions of added Cu desorbed during 10 desorption periods were low, ranging from 2.5% in the 24‐h to 6% in the 2‐h desorption periods. The desorption of Cu decreased with increasing soil pH. The irreversible retention of Cu might be the result of complex formation with Cu at high pH.     

某极度酸化的酸性硫酸盐土壤中可溶性和交换性酸的特征

An extremely acidified acid sulfate soil(ASS) was investigated to characterise its soluble and exchangeable acidity,The results showed that soluble acidity of a sample dtermined by titration with a KOH soulution was much significantly greater than that indicated by pH measured using a pH meter,paricularly for the extremely acidic soil samples,This is because the total soluble acidity of the extremely acidic soil samples was mainly composed of various soluble Al and Fe species,possibly in forms of Al sulfate complexes(e.g.,AlSO4^ ) and feerous Fe(Fe^2 )_,It is therefore suggested not to use pH alone as an indicator of soluble acidity in ASS,particularly for extremely acidic ASS,It is also likely that AlSO4^ actively participated in cation exchange reactions.It appears that the possible involvement of this Al sulfate cation in the cation adsorption has significant effect on increasing the amount of acidity being adsorbed by the soils.     

Soil Retention Capacity of Phenols from Biologically Pre-Treated Kraft Mill Wastewater

Allophanic soil, natural and activated by acidification or calcination was used to adsorb organic recalcitrant compounds (lignin and chlorophenols) from biologically pre-treated kraft mill effluent. A synthetic non crystalline aluminosilicate like allophane coated with iron oxide (Al-Si-Fe) was used as control for comparison purposes. It was observed that the adsorption capacity of the allophanic soil increased at higher solid/solution ratio, and at lower pH values. The highest total phenolic compounds removal was obtained between pH 4.0 and 4.5 for natural and activated soil using a solid/solution ratio of 1:5, and for synthetic aluminosilicate using 300 mg in 30 mL of effluent solution. Soil activated by calcination procedure presented the highest total phenolic compounds adsorption capacity (71–85%) for untreated and aerobic or anaerobic pre-treated effluent. The specific chlorophenols analysis indicated that pentachlorophenol (PCP) was almost completely adsorbed onto the allophanic soil (> 99%), and that over 79% of the 2,3,4,6-tetrachlorophenol (TeCP) was adsorbed, independent of the biological pre-treatment type and the soil activation procedure. On the other hand, 2,4-dichlorophenol (DCP) coming from both aerobic and anaerobic treated effluent was poorly removed (24–30%) when natural soil was used for adsorption; whereas in calcinated and acidified soil DCP removal was more than 71%.     

pH对砖红壤和黄棕壤Cu~(2+)吸附与解吸的影响

对砖红壤和黄棕壤在不同浓度、不同pH下吸附和解吸Cu2+进行了测定。结果表明, 2种土壤Cu2+吸附量均随平衡液中Cu2+浓度增加而增大,两者关系较好地符合Langmuir吸附方程。Cu2+吸附量随pH升高而增加,Cu2+分配系数的对数与pH呈极显著的线性正相关,吸附一个Cu2+所释放H+的平均数砖红壤(1. 19)大于黄棕壤(1. 01)。可解吸Cu2+的数量随pH升高和吸附Cu2+的数量增加而增加,在pH4~6下,黄棕壤吸附Cu2+及可解吸Cu2+的比例(平均为10. 5% )大于砖红壤(平均为3. 1% )。由此认为, 2种土壤吸附Cu2+虽以专性吸附为主,但砖红壤的表面吸附点位较少,专性吸附点位的比例较高,对Cu2+的亲和性或专性吸附性大于黄棕壤。     

长期秸秆还田下土壤铵态氮的吸附解吸特征

【目的】研究长期秸秆还田对不同轮作区域耕层和亚耕层的土壤铵态氮 (NH₄+) 的吸附、解吸特征差异,通过 Langmuir 等温吸附方程拟合得到 NH₄+ 最大吸附量 (q_max) 和吸附系数 (b),分析长期秸秆还田对不同土壤 NH₄+ 的吸附、解吸特征差异及影响因素。 【方法】2015 年 10 月水稻收获后,在湖南望城 (稻–稻轮作)、江西进贤 (稻–稻轮作)、重庆北碚 (稻–麦轮作) 三个长期定位试验点 (25 年) 采集不施肥 (CK)、长期施用化肥 (NPK) 和长期秸秆还田配施化肥 (NPKS) 三个处理、0—20 cm 和 20—40 cm 两个土层的土样,进行土壤 NH₄+ 的吸附–解吸室内试验,吸附试验为添加不同浓度的 NH₄Cl 溶液振荡、离心后,测定滤液 NH₄+ 浓度;解吸试验采用吸附试验后的土壤样品,经无水乙醇淋洗至无 NH₄+ 后,再加入 0.01 mol/L 的 KCl 溶液振荡、离心后测定滤液 NH₄+ 浓度。 【结果】长期秸秆还田对不同试验点土壤 NH₄+ 吸附–解吸特征的影响差异较大。处理间的差异主要表现在耕层土壤。当平衡溶液 NH₄+ 浓度 < 400 mg/L 时,不同试验点耕层和亚耕层处理间差异均不明显;当平衡溶液浓度 > 400 mg/L 时,处理间耕层土壤对 NH₄+ 吸附表现出差异,其中望城试验点土壤对 NH₄+ 的吸附表现为 CK > NPK > NPKS,北碚试验点则表现为 CK > NPKS > NPK,且北碚试验点的紫色土对 NH₄+ 的吸附显著高于望城和进贤试验点的红壤性水稻土。进贤试验点不同处理间差异不明显,且土壤对 NH₄+ 的吸附量最低。 通过相关性分析发现,q_max和土壤 pH、阳离子交换量 CEC 呈显著正相关,而与土壤有机质和全氮含量呈显著负相关;b 与土壤性质的相关性与q_max 则相反。从土壤对 NH₄+ 的解吸曲线来看,耕层和亚耕层土壤对 NH₄+ 的解吸在各试验点不同处理间均表现为差异不显著,其中望城和进贤试验点的红壤性水稻土 NH₄+ 的最大解吸量高于其吸附量,而北碚试验点的紫色土 NH₄+ 的最大解吸量 (541.89～742.38 mg/kg) 则远低于其吸附量 (1003.83～2014.79 mg/kg)。 【结论】长期秸秆还田对不同土壤 NH₄+ 的吸附–解吸作用影响不同,对于土壤吸附位点较多且钾离子含量丰富的紫色土而言,长期秸秆还田有利于土壤对氮的吸附;而对于土壤偏酸性的红壤性水稻土而言,长期秸秆还田则可能因为增加了土壤有机质含量而减少了土壤对铵态氮的吸附位点,从而降低了土壤对氮的吸附保持能力。     

Effect of phosphogypsum application on the chemical properties of Andosols,and the growth and Ca uptake of melon seedlings

Abstract

Allophanic Andosols are widely used as a major material in commercial nursery media for fruit vegetables in Japan because of their remarkable physical properties, such as a high water-holding capacity. In the present study, our objectives were: (1) to examine the effect of phosphogypsum (PG) on the chemical properties of Andosols, (2) to investigate the effect of PG on the growth and Ca uptake of melon seedlings. The effect of PG on chemical properties of Andosols was studied using five Andosols with different inorganic and organic colloidal components. The change in soil pH (H₂O) was dependent on the soil samples; an increase was observed in the case of Kawatabi 3Bw soil; a sharp decrease in Kawatabi A2 soil; and almost no change or a slight decrease in Kameoka A1, A2 and Bw soils. The water-soluble Ca content was examined as an index of Ca availability in Andosols treated with PG. The increment in water-soluble Ca by PG application was depressed by allophane. The effect of PG application to the nursery media prepared from Andosols on growth and Ca uptake of melon (Cucumis melo L.) was examined in 2002. Three different varieties, Amusu, Earl's and Midorishima, were used in this experiment. The pH value of nursery media was stable at 6.4 ± 0.1 regardless of PG application rate. In contrast, electrical conductivity was clearly increased by PG application, and was reached at 1.2 dS m^?1 in 4.0 g L^?1 application. The application of PG increased water soluble Ca of nursery media from 1.7 to 5.2 cmol_c L^?1. Both top and root growth of melon seedlings were enhanced regardless of varieties, dry matter weights were maximized at 4 g L^?1 PG application. The Ca uptake of melon seedlings was promoted by PG application in all the varieties. It was suggested that the relative root growth rate of melon seedlings was closely related to the Ca uptake of melon seedlings.     

The effect of pH on zinc adsorption by a lateritic soil in the presence of citrate and oxalate

A change in the pH of the rhizosphere may alter the effect that organic ligands have on the concentration of Zn in the soil solution. To assess this effect, Zn adsorption by a lateritic soil was measured in the presence of 0, 1 and 3 mM of citrate and oxalate at nine values of pH ranging from pH 2 to 8. The concentrations of Zn and the ligands remaining in the solution were determined after 17 h shaking with the soil at soil:liquid ratio of 1:5. Subsequently, Zn speciation was calculated. The effectiveness of an organic ligand (L) in changing Zn adsorption was influenced by the sign of the charge of the Zn-L complex, the point of zero salt effect (PZSE) of the soil, the pH of the soil solution and the quantity of the complex formed. When the pH was above the PZSE of the soil, citrate decreased Zn adsorption by up to 38% whereas it increased Zn adsorption by as much as 51 % when the pH was below the PZSE. Oxalate had a similar but smaller effect than citrate under the conditions of the experiment. Zn adsorption was correlated with the concentration of zinc citrate in both pH regions (r2>0.98) and with oxalate above pH 2.7. The increase in Zn adsorption at low pH could have been caused by the adsorption of negatively charged Zn-L complexes.     

Studies on the sorption of I− (iodide) and IO3 − (iodate) onto Andosols

In order to understand the sorption phenomena of I on Andosols, one of the most typical soils in Japan, radiotracer experiments were carried out using I^? (iodide), IO₃ ^? (iodate), and for comparison, Cl^?(chloride) by the batch method, with special emphasis on the influence of solution pH and concentration of the respective ions. Kanuma soil composed of allophane, one of the main consistent minerals in most Andosols, was also examined regarding sorption. The sorption of I^? and Cl^? on Kanuma soil increased with decreasing pH and the sorptions were expressed by Henry isotherms. This indicated that these anions were electrostatically adsorbed on the positive charges which appeared on the surface of Kanuma soil. Sorption of Cl^? onto Andosol could also be explained by electrostatic adsorption. Both I^? and IO₃ ^? were readily sorbed on Andosol from water even under weakly alkaline conditions. The adsorption isotherm of IO₃ ^? on Andosol almost overlapped with that on Kanuma soil, suggesting that the high IO₃ ^? sorption on Andosol was caused by the high adsorbability of IO₃ ^?on allophane and/or sesquioxides of Fe and Al. However, the high I^? sorption on Andosol could not be explained analogously.     

Andosol to Luvisol evolution in Central Mexico: timing, mechanisms and environmental setting

Surface and buried Andosols and buried Luvisols of the Nevado de Toluca Late Quaternary tephra-paleosol sequence (Central Mexico) were studied to show whether these soils present an evolutionary sequence and to determine the pedogenic mechanisms and environmental factors involved in the evolutionary process. Micromorphological observations and mineralogical composition of fine sand and clay fractions were used to detect type and succession of soil-forming process. Some of the buried Andosols, defined as “intergrade” Andosols, have a predominantly blocky structure, humus-depleted areas, redoximorphic features and thin clay coatings in Ah horizons. Clay fractions of buried Andosols contain halloysite besides amorphous components, whereas in modern Andosols, allophane is dominant. Luvisols have micro-areas with granular structure and abundant phytoliths in the groundmass of Bt horizons assumed to be the relict Andosol features. Luvisol clay fractions are dominated by halloysite and kaolinite. Primary minerals show micromorphological weathering features in all studied soils being stronger in Luvisols; however, even in Luvisols, sand fractions consist mostly of unstable volcanic silicates. We hypothesise that the studied profiles form an evolutionary sequence: Andosols–“intergrade” Andosols–Luvisols; the soil transformation is supposed to be linked to progressive crystallisation of 1:1 clay minerals. Comparing the Nevado de Toluca paleosol properties with the existing data on volcanic soil climo- and chronesequences and assessing the regional paleopedological and lacustrine records of Quaternary paleoclimates, we concluded that wet/dry climatic oscillations took place during the formation of the studied paleosols. Rapid crystallisation of 1:1 minerals occurred during dry phases, which speeded up the Andosol to Luvisol transformation and made it independent from the primary mineral weathering status. The Andosol to Luvisol transformation accelerated by climatic fluctuations is thought to be a common soil evolutionary pathway in the subtropical and tropical regions of recent volcanism, which suffered contrasting precipitation oscillations in the Quaternary.     

Distribution of Zinc,Manganese, Copper,Cobalt, and Nickel in Andosols Profiles

The distribution of zinc, manganese, copper, cobalt, and nickel in Andosols was investigated. Sixty nine soil samples were collected from different horizons of an Andosols profile in Miyakonojo Basin in south Kyushu, Japan, The total contents of heavy metals were determined by digestion and four extraction solutions, 1 M NH₄Ac (ammonium acetate) pH 4.5, 0.1 M HCl, 0.01 M EDTA (ethylenediaminetetraacetic acid) pH 6.5, and 0.005 M DTPA (diethylenetri-aminepentaacetic acid) pH 7.3 were used to determine the contents of available Zn, Mn, Cu, Co, and Ni in Andosols in relation to the organic carbon content. The results of the extraction analysis showed that by the use of 0.1 M H Cl high value of extracted heavy metals in the upper layers of the humus horizons were obtained while EDTA extraction yielded a large amount of the above mentioned metals in the high humus horizons. The extractable heavy metals contents were high and these metals closely related to the organic carbon content mostly in the humus horizons in the profile. Where, biocycling process may play an important role in the concentration of heavy metals. Based on the study, it was found that the total content of Zn increased towards the C horizons or pumice layers in the soil profile. Such a trend was also found in the case of the Mn content. While the Cu content in the humus horizons was much higher in the upper part of each humus horizon. According to this study the distribution of heavy metals, Cu (organic matter complexes) in the Andosols profile was more stable than that of Zn (organic matter complexes) in soils. It was shown that Zn in the surface humus horizon was enriched but that some amount was leached under buried conditions. The same phenomenon was also observed in the distribution of Mn in the profile. The movement of Co and Ni in the soil profile was limited, as evidenced by the sharp reduction in the concentrations of these two metals in buried soils.

Hence, it is concluded that the distribution of Zn, Mn, Cu, Co, and Ni was considerably higher in the humus horizons of the Andosols profiles.     

Formation of bound residues of 8-hydroxybentazon by oxidoreductive catalysts in soil

This study was performed to determine which oxidoreductive catalysts were most efficient in catalyzing the binding of 8-hydroxybentazon to soil humic substances. 8-Hydroxybentazon was completely transformed by an oxidoreductive enzyme, laccase of Myceliophthora thermophila, at pH 3.0-7.0 within 30 min. When abiotic catalysts, manganese(IV), iron(III), and aluminum oxides were used in the same pH range, 8-hydroxybentazon was completely transformed only by manganese(IV) oxide (delta-MnO2), but a relatively small amount of 8-hydroxybentazon was transformed by iron(III) oxide and aluminum oxide. The adsorption of 8-hydroxybentazon in the soil showed an H-type and coincided well with the Langmuir isotherm. To better understand the factors involved in the rapid and strong binding of 8-hydroxybentazon with soil humic substances, 8-hydroxybentazon transformation by oxidoreductive catalysts was studied in various soil conditions: air-dried, preincubated, sterilized, and iron(III) oxide and manganese(IV) oxide free. 8-Hydroxybentazon was completely transformed within 24 h in the decreasing order of preincubated, air-dried, and sterilized soils. However, little transformation was observed in the iron(III) oxide and manganese(IV) oxide free soils. These results suggest that the major catalyst responsible for the rapid and strong binding of 8-hydroxybentazon to soil humic substances is a metal oxide, manganese(IV) oxide, not a soil oxidoreductive enzyme.