米渣蛋白对镉的吸附效果及其对土壤中镉的钝化作用研究

为探究米渣蛋白对水溶液中镉的吸附效果及米渣对土壤中镉活性的钝化效果,该研究首先用米渣蛋白在水溶液中对镉进行吸附、用盐酸解吸,并用Langmuir、Freundlich等温吸附方程来拟合米渣蛋白在水溶液中对镉的吸附过程,用动力学方程研究米渣蛋白与镉结合的机理,并根据线性关系从准一级、准二级吸附动力学方程中筛选更接近吸附动力的拟合方程。其次,通过周期取样,用Tessier分步连续提取法测定并探究米渣对土壤中镉的钝化能力。研究结果表明:在不同初始质量分数的镉溶液中米渣对镉的最大吸附量13.28mg/g,用盐酸解吸各初始质量分数下结合的镉,解吸率均达到90%以上。同时,Langmuir和Freundlich等温方程均能拟合米渣蛋白在水溶液中对镉的吸附过程,且R2达到0.99以上;准一级动力学、准二级动力学方程拟合结果是,拟合出的准二级动力学方程线性更好,米渣蛋白对镉的吸附动力更符合准二级动力学方程。土壤中镉钝化试验表明:加入米渣后,28d内土壤中镉的钝化效果较好,可能是由于米渣中的蛋白改变了土壤中镉的存在状态并降低镉的活性所致。该研究结果为米渣的应用提供新的思路,可为其在废水除镉、镉污染土壤的修复等方面应用提供理论依据。     

施用碱稳定污泥污水土壤经γ-辐照后土壤溶液中Cu和Zn

Soil samples collected from several acid soils in Guangdong, Fujian, Zhejiang and Anhui provinces of the southern China were employed to characterize the chemical species of aluminumions in the soils. The proportion of monomeric inorganic Al to total Al in soil solution was in the range of 19% to 70%, that of monomeric organic Al (Al-OM) to total Al ranged from 7.7% to 69%, and that of the acid-soluble Al to total Al was generally smaller and was lower than 20% in most of the acid soils studied. The Al-OM concentration in soil solution was positively correlated with the content of dissolved organic carbon (DOC) and also affected by the concentration of Al³⁺. The complexes of aluminum with fluoride (Al-F) were the predominant forms of inorganic Al, and the proportion of Al-F complexes to total inorganic Al increased with pH. Under strongly acid condition, Al³⁺ was also a major form of inorganic Al, and the proportion of Al³⁺ to total inorganic Al decreased with increasing pH. The proportions of Al-OH and Al-SO₄ complexes to total inorganic Al were small and were not larger than 10% in the most acid soils. The concentration of inorganic Al in solution depended largely on pH and the concentration of total F in soil solution. The concentrat ions of Al-OM, Al³⁺, Al-F and Al-OH complexes in topsoil were higher than those in subsoil and decreased with the increase in soil depth. The chemical species of aluminumions were influenced by pH. The concentrations of Al-OM, Al³⁺, Al-F complexes and Al-OH complexes decreased with the increase in pH.     

The relationship of readily decomposable organic matter of the paddy soil to its colloidal complexes

The soil nitrogen of paddy soil is found to exist in the form of organic and inorganic nitrogen. In general, the content of inorganic nitrogen is so low that it is mainly occupied by organic nitrogen. Such soil organic nitrogen is characterized by large resistance to decomposition by soil microorganisms, and so its mineralization occurs to a small extent in most cases. However, as revealed by M. Shioiri¹⁾ and T. Harada et al. ^2,3), by some appropriate treatment of paddy soil, a part of soil organic nitrogen becomes decomposed by microorganisms and mineralized under flooded condition. Among various treatment, for example, are Presented the followings: (1) air-drying of soil Prior to flooding; (2) raising the soil temperature during the flooded condition; (3) raising the soil reaction (pH 9.0) by addition of weak alkali solution; (4) the addition of neutral salts such as Nafiuoride, Na-phosphate, Na-oxalate etc., which make soil humus peptizable.     

Formation of Tebuconazole Complexes with Cadmium(II) Investigated by Electrospray Ionization Mass Spectrometry

The formation of complexes between tebuconazole (Teb) and cadmium in simplified model solutions as well as soil solutions was studied using electrospray ionization mass spectrometry. Teb and cadmium form two types of complexes with the general formulas [Cd(Teb) _n ]²⁺ (n?=?1?C4) and [CdI(Teb) _m ]⁺ (m?=?1?C3), where iodine corresponds to the counterion used. The most intense Teb/cadmium complex is [CdI(Teb)₂]⁺, and the most stable one is [Cd(Teb)(Teb ? H)]⁺. Another detected complex, the dication [Cd(Teb)₄]²⁺, was considered as the origin complex for the iodine-free complexes and was found in a sample prepared from forest soil solution naturally contaminated with cadmium ions.     

电解质对酸性土壤铝的溶解及铝形态在土壤溶液中的分布的影响

KCl, CaCl₂, NH₄Cl, NaCl, K₂SO₄ and KF solutions were used for studying the effects of cations and anions on the dissolution of aluminum and the distribution of aluminum forms respectively. Power of exchanging and releasing aluminum of four kinds of cations was in the decreasing order Ca²⁺ >K⁺ >NH₄⁺ >Na⁺. The dissolution of aluminum increased with the cation concentration. The adsorption affinity of various soils for aluminum was different. The aluminum in the soil with a stronger adsorption affinity was difficult to be exchanged and released by cations. The Al-F complexes were main species of inorganic aluminum at a low concentration of cations, while Al³⁺ became major species of inorganic aluminum at a high concentration of cations. The results on the effect of anions indicated that the concentrations of total aluminum, three kinds of inorganic aluminum (Al³⁺, Al-F and Al-OH complexes) and organic aluminum complexes (Al-OM) when SO₄^2- was added into soil suspension were lower than those when Cl^- was added. The dissolution of aluminum from soils and the distribution of aluminum forms in solution were affected by the adsorption of F^- on the soil. For soils with strong affinity for F^-, the concentrations of the three inorganic aluminum species in soil solution after addition of F^- were lower than those after addition of Cl^-; but for soils with weak affinity for F^-, the concentrations of Al³⁺ and Al-OM were lower and the concentrations of Al-F complexes and total inorganic aluminum after addition of F^- were higher than those after addition of Cl^-. The increase of F^- concentration in soil solution accelerated the dissolution of aluminum from soils.     

镉污染中性土壤伴矿景天修复的硫强化及其微生物效应

采用田间微区试验研究了施硫处理对中性镉污染农田上伴矿景天镉吸取修复效率、土壤p H、有效态镉、有效态硫以及微生物群落变化的影响。结果发现:土壤p H随时间和硫用量的增加而显著下降,有效态镉和有效态硫含量随时间和硫用量的增加而显著增加。在360 g/m²硫处理下,伴矿景天地上部镉含量为70.9 mg/kg,较不施硫对照(38.3 mg/kg)增加85.1%,耕层土壤全量镉去除率为19.4%,是对照(10.5%)的1.85倍。施硫处理150 d后,土壤Thiomonas和Rhodanobacter细菌相对丰度显著高于试验前土壤和对照处理。本试验结果表明,中性土壤施加适量硫磺不仅可显著提高污染土壤中镉的生物有效性,也可通过调节与硫代谢相关的功能微生物,显著增强镉的植物吸取修复效率。     

Factors affecting the soil sorption of iodine

Iodine-129 is an important radionuclide released from nuclear facilities because of its long radioactive half-life and its environmental mobility. Its retention in surface soils has been linked to pH, organic matter, and Fe and Al oxides. Its inorganic solution chemistry indicates I will most likely exist as an anion. Three investigations were carried out to provide information on the role of the inorganic and organic chemistry during sorption of I by soil. Anion competition using Cl^? showed that anion exchange plays a role in I sorption in both mineral and organic soils. The presence of Cl decreased the loss of I^? from solution by 30 and 50% for an organic and a carbonated sandy soil respectively. The I remaining in solution was associated primarily with dissolved organic carbon (DOC). The loss rate from solution appears to depend on two reactions of I with the soil solids (both mineral and organic) creating both a release to and a loss from solution, and the reaction of I with the DOC (from very low to high molecular weight). Composition analyses of the pore water and the geochemical modelling indicate that I sorption affects the double-charged anion species in solution the most, particularly SO₄ ^?. Iodide introduced to natural bog groundwater at three concentrations (10^?3, 10^?1 and 10 meq L^?1) remained as I^? and was not lost from solution quickly, indicating that the association of I with DOC is slow and does not depend on the DOC or I concentration. If sorption of I to soil solids or DOC is not sensitive to concentration, then stable I studies, which by necessity must be carried out at high environmental concentrations, can be linearly extrapolated to radioactive I at much lower molar concentrations.     

Fluorescence detection of aluminum in arbuscular mycorrhizal fungal structures and glomalin using confocal laser scanning microscopy

Arbuscular mycorrhizal spores and glomalin-related soil protein (GRSP) isolated from acid soils were analyzed using confocal laser scanning microscopy (CLSM) for Al detection. Mycorrhizal structures of Glomus intraradices produced under in vitro conditions as well as spores and GRSP from neutral and Cu-polluted soils were used as contrasting criteria. Spores and GRSP from soils with 7 and 70% Al saturation showed autofluorescence which increased especially at the highest soil Al level and when Al³⁺ solution was added. G. intraradices spores showed fluorescence only when exogenous Al³⁺ was added. On the contrary, spores and GRSP from neutral and Cu-polluted soils showed little or no significant fluorescence. This fluorescence shown by fungal structures and GRSP when subjected to high Al (of endogenous or exogenous origin) suggest a high capacity for Al immobilization, which could be an effective way to reduce Al activity and phytotoxicity in acid soils.     

Distribution of mercury species in soil from a mercury-contaminated site

The distribution of mercury species was determined in soil from a site with Hg contamination. Mercury contamination was primarily confined to the top 40 cm of soil, and the concentration of total Hg ranged from 0.5 to 3000 µg Hg g^?1. Of total Hg present, we determined that 91% was inorganic, 0.01% organic (as methyl Hg), and 6% elemental Hg. Furthermore, of total inorganic Hg present, 85% was in the insoluble mercuric sulfide form. Thus, of total Hg present in soil at this contaminated site, 91% was in the relatively insoluble HgS and Hg⁰ forms.     

An evaluation of some manual colorimetric methods for the determination of inorganic nitrogen in soil extracts

Abstract

A number of manual colorimetric methods for the determination of inorganic nitrogen in 1 M KCl soil extracts were investigated to find techniques that were inexpensive, rapid, versatile and suitable for laboratories with limited analytical equipment. Three colorimetric methods for No^? ₃‐N determination were evaluated and only the copperised/cadmium reduction technique suffered no significant interference from the Cl^? present in the extracting solution. A phenol‐hypo‐chlorite (Berthelot) procedure for NH⁺ ₄‐N determination and the Griess‐Ilosvay method for NO^? ₂‐N determination were both found suitable for N determination in 1M KC1 soil extracts. The reliability and accuracy obtainable with the manual colorimetric methods described was shown to be comparable with that obtained from colorimetric analyses performed using an AutoAnalyser.     

Nutrients in a calcareous soil affected by Cadmium

A calcareous soil (Haploxeroll calcic) was amended in two different forms according with the standard nutritional requirements of tomato plant. The treatments applied were: i) an organic fertilization applying sewage sludge (SS), ii) an inorganic fertilization (IN) using mineral fertilizers (NPK), and iii) a treatment called W where no fertilizer was applied. For each treatment, cadmium (Cd) pollution was added to the soil establishing different concentrations (0, 3, 30 and 100 mg kg^‐1 d.w.). The availability of macronutrients and micronutrients were analyzed in the soil. Phosphorus (P), iron (Fe), and copper (Cu) were the nutrients more affected by Cd. In general, sewage sludge favored the availability of nutrients in the same degree of the inorganic fertilization.     

Do plant species with different growth strategies vary in their ability to compete with soil microbes for chemical forms of nitrogen?

We used dual labelled stable isotope (¹³C and ¹⁵N) techniques to examine how grassland plant species with different growth strategies vary in their ability to compete with soil microbes for different chemical forms of nitrogen (N), both inorganic and organic. We also tested whether some plant species might avoid competition by preferentially using different chemical forms of N than microbes. This was tested in a pot experiment where monocultures of five co-existing grassland species, namely the grasses Agrostis capillaris, Anthoxanthum odoratum, Nardus stricta, Deschampsia flexuosa and the herb Rumex acetosella, were grown in field soil from an acid semi-natural temperate grassland. Our data show that grassland plant species with different growth strategies are able to compete effectively with soil microbes for most N forms presented to them, including inorganic N and amino acids of varying complexity. Contrary to what has been found in strongly N limited ecosystems, we did not detect any differential uptake of N on the basis of chemical form, other than that shoot tissue of fast-growing plant species was more enriched in ¹⁵N from ammonium-nitrate and glycine, than from more complex amino acids. Shoot tissue of slow-growing species was equally enriched in ¹⁵N from all these N forms. However, all species tested, least preferred the most complex amino acid phenylalanine, which was preferentially used by soil microbes. We also found that while fast-growing plants took up more of the added N forms than slow-growing species, this variation was not related to differences in the ability of plants to compete with microbes for N forms, as hypothesised. On the contrary, we detected no difference in microbial biomass or microbial uptake of ¹⁵N between fast and slow-growing plant species, suggesting that plant traits that regulate nutrient capture, as opposed to plant species-specific interactions with soil microbes, are the main factor controlling variation in uptake of N by grassland plant species. Overall, our data provide insights into the interactions between plants and soil microbes that influence plant nitrogen use in grassland ecosystems.     

Fluorescence detection of aluminum in arbuscular mycorrhizal fungal structures and glomalin using confocal laser scanning microscopy

Arbuscular mycorrhizal spores and glomalin-related soil protein (GRSP) isolated from acid soils were analyzed using confocal laser scanning microscopy (CLSM) for Al detection. Mycorrhizal structures of Glomus intraradices produced under in vitro conditions as well as spores and GRSP from neutral and Cu-polluted soils were used as contrasting criteria. Spores and GRSP from soils with 7 and 70% Al saturation showed autofluorescence which increased especially at the highest soil Al level and when Al³⁺ solution was added. G.intraradices spores showed fluorescence only when exogenous Al³⁺ was added. On the contrary, spores and GRSP from neutral and Cu-polluted soils showed little or no significant fluorescence. This fluorescence shown by fungal structures and GRSP when subjected to high Al (of endogenous or exogenous origin) suggest a high capacity for Al immobilization, which could be an effective way to reduce Al activity and phytotoxicity in acid soils.     

Development of liquid chromatography mass spectrometry method for analysis of organic N monomers in soil

The aim of this study was to develop an analytical procedure based on liquid chromatography-mass spectrometry (LC–MS) for analysis of monomeric organic N compounds in soil extracts. To benchmark the developed LC–MS method it was compared with a capillary electrophoresis–mass spectrometry (CE–MS) method recently used for analysis of small organic N monomers in soil. The separation was optimized and analytical performance assessed with 69 purified standards, then the LC–MS method was used to analyse soil extracts. Sixty-two out of 69 standards were analysable by LC–MS with separation on a hydrophilic interaction liquid chromatography column. The seven compounds that could not be analysed were strongly cationic polyamines. Limits of detection for a 5 μL injection ranged between 0.002 and 0.38 μmol L⁻¹, with the majority (49 out of 62) having limits of detection better than 0.05 μmol L⁻¹. The overall profile and concentration of small organic N monomers in soil extracts was broadly similar between LC–MS and CE–MS, with the notable exception of four ureides that were detected by LC–MS only. In soil extracts that had been concentrated ten-fold the detection and quantification of (some) organic N compounds was compromised by the presence of large amounts of inorganic salts. The developed LC–MS method offered advantages and disadvantages relative to CE–MS, and a combination of the two methods would achieve the broadest possible coverage of organic N in soil extracts.     

Forms and Uptake of Manganese in Relation to Soil Taxonomic Orders in Alluvial Soils of Punjab,India

Different forms of manganese (Mn) were investigated, including total, diethylenetriamine penta-acetic acid (DTPA) extractable, soil solution plus exchangeable (Mn), Mn adsorbed onto inorganic sites, Mn bound by organic sites, and Mn adsorbed onto oxide surfaces, from four soil taxonomic orders in northwestern India. The total Mn content was 200–950 mg kg^?1, DTPA-extractable Mn content was 0.60–5.80 mg kg^?1, soil solution plus exchangeable Mn content was 0.02–0.80 mg kg^?1, Mn adsorbed onto inorganic sites was 2.46–90 mg kg^?1, and Mc adsorbed onto oxide surfaces was 6.0–225.0 mg kg^?1. Irrespective of the different fractions of Mn their content was generally greater in the fine-textured Alfisols and Inceptisols than in coarse-textured Entisols and Aridisols. The proportion of the Mn fractions extracted from the soil was in the order as follows: Adsorbed onto oxide surfaces > adsorbed onto inorganic site > organically bound > DTPA > soil solution + exchangeable. Based on coefficient of correlation, the soil solution plus exchangeable Mn, held onto organic site and oxide surface (amorphous) and DTPA-extractable Mn, increased with increase in organic carbon of the soil. The two forms, adsorbed onto inorganic site (crystalline) and DTPA extractable, along with organic carbon, increased with increase in clay content of the soil. DTPA-Mn and Mn adsorbed onto oxide surfaces and held on organic site decreased with increased with an increase in calcium carbonate and pH. Total Mn was strongly correlated with organic carbon and clay content of soil. Among the forms, Mn held on the organic site, water soluble + exchangeable and adsorbed onto oxide surface were positively correlated with DTPA-extractable Mn. DTPA-extractable Mn seems to be a good index of Mn availability in soils and this form is helpful for correction of Mn deficiency in the soils of the region. The uptake of Mn was greater in fine-textured Inceptisols and Alfisols than in coarse-textured Entisols and Aridisols. Among the different forms only DTPA-extractable Mn was positively correlated with total uptake of Mn. Among soil properties Mn uptake was only significantly affected by pH of the soil.     

冻融作用对土壤中重金属镉赋存形态的影响

选择东北地区典型土壤-棕壤作为供试土壤,在室内培养条件下,采用逐级提取法,通过逐步回归分析研究了冻融作用对镉在土壤中赋存形态的影响。结果表明:土壤中添加外源重金属镉后,不同形态镉的含量差异很大,在本试验条件下镉主要以交换态为主,其次为残渣态,有机结合态、铁锰氧化物结合态含量相对较低;在冻融作用下,水分和冻融频次对各形态镉含量的影响达到了极显著水平(P<0.01);利用逐步回归分析建立了水分和冻融频次对不同形态镉含量影响的最优回归方程。     

Quantification of pyrophosphate in soil solution by pyrophosphatase hydrolysis

A commercial pyrophosphatase from Saccharomyces cerevisiae selectively hydrolyzed sodium pyrophosphate, but showed no significant activity towards a range of other organic and condensed inorganic phosphorus compounds. Pyrophosphate determined by pyrophosphatase hydrolysis accounted for 38 ± 12% (mean ± standard error of 19 sites) of the non-reactive phosphorus in soil solution obtained by centrifugation from a series of lowland tropical rain forest soils. Pyrophosphate concentrations were up to 89 μg P l⁻¹ and correlated positively with microbial phosphorus, soil solution pH, and native phosphomonoesterase activity in soil solution, but not with total soil pyrophosphate determined by NaOH–EDTA extraction and solution ³¹P NMR spectroscopy. In summary, we identify pyrophosphate as a major constituent of soil solution phosphorus in lowland tropical rain forests, and demonstrate that a commercial pyrophosphatase can be used as a selective tool to quantify trace concentrations of pyrophosphate in soil solution.     

Modelling changes in cations in the topsoil of an Amazonian Acrisol in response to additions of wood ash

Predictions of changes in soil solution chemistry and exchangeable cations which occur on ash deposition after slash burning are complex and may be facilitated by the use of chemical models. Multi-ion sorption in the topsoil of an Amazonian Acrisol was studied by sequentially adding small amounts of electrolytes to soil and mixtures of soil and ash in batch experiments. A chemical equilibrium model that included inorganic complexation, multiple cation exchange and sparingly soluble salts (aluminium hydroxide and magnesian calcites) was used to interpret the results. The model predicted well the pH and sorption values in all experiments in which there was no addition of ash. The model suggested that cation exchange was the main process determining concentrations of soil solutions in all cases where neutral salt solutions were added, and that proton buffering was achieved by the dissolution of Al(OH)₃ which was followed by Al³⁺ adsorption. Calculation of ion activity products in solutions from various batch experiments in soil + ash mixtures suggested that magnesian calcites of differing solubility may be in equilibrium with the activities of Mg²⁺ and Ca²⁺ in solution. An incongruent dissolution of Mg resulted in less soluble magnesian calcites in the ash. The model estimated satisfactorily the pH and the sorption of ions for all experiments with differing ash additions to the soil. Most of the Ca and significant amounts of Mg added in the ash are expected to remain for a long time in the soil and may determine the Ca and Mg status of the soil solution, primarily controlled by principles of solubility products.     

Measurement of the fate of acetic acid form carbon in soil solution of flooded soils using high performance liquid chromatography coupled with isotope ratio mass spectrometry

Carbon-14 (¹⁴C) which can be taken into low molecular weight organic compounds (e.g. acetic acid, formic acid, methanol and ethanol) is one of the most important radionuclides released from transuranic waste disposal sites. To understand the fate of organic compounds in the soil environment, a stable carbon isotope, ¹³C, can be used as a tracer of ¹⁴C. In this study, ¹³C-labeled acetic acid was added to six soil-water mixture samples and the chemical form changes in the soil solutions were measured by high performance liquid chromatography coupled with isotope ratio mass spectrometry. The ¹³C-labeled acetic acid in the soil solutions was detected for the first 24 h, but could not be detected afterwards for any soil samples. Thus, in any soils that have similar properties to the soil samples used in the present study, most of the ¹³C-labeled acetic acid would likely be changed to other physico-chemical forms and be removed from the soil solutions in a very short time period. Less than 3% of the carbon added as acetic acid remained in the soil solutions, and was possibly mainly in inorganic forms. Carbon from acetic acid would not be retained in soil solutions for 48 h.     

改良剂对滴灌棉田镉分布及迁移特征的影响

通过田间桶栽试验研究了高浓度镉(40mg/kg)条件下,4种改良剂(有机—无机复合稳定剂、无机高分子复配材料、聚丙烯酸盐复配材料、有机高分子复配材料)对棉田土壤剖面中土壤pH、阳离子交换量(CEC)、镉含量及其形态分布迁移的影响。结果表明:(1)4种改良剂均显著提高了棉田土壤剖面各层的pH和CEC,无机高分子复配材料在0—20cm土层效果最好,分别增加了0.43个单位和4.43cmol/kg;(2)改良剂促进土壤可交换态镉向其余4种形态的转化,相关分析表明碳酸盐结合态与可交换态镉含量呈极显著负相关(P0.01),在0—20cm和20—40cm土层中效果尤为突出,以无机高分子复配材料对土壤可交换态镉的降低效果最好,降低了3.61mg/kg;(3)各土层中的pH和CEC均与可交换态镉呈负相关,与其他形态呈正相关。即改良剂通过改变土壤pH和CEC,影响土壤镉的分布及迁移,从而降低镉的有效性,达到改善土壤环境的目的。