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1.
施用碱稳定固体的酸性土壤的Cu和Zn的形态分布   总被引:2,自引:1,他引:2  
LUO Yong-Ming 《土壤圈》2002,12(2):165-170
Fractionation of metals in a granite-derived acid sandy loam soil amended with alkaline-stabilised sewagesIudge biosolids was conducted in order to assess metal bioavailability and environmental mobility soil solution was extracted by a centrifugation and filtration technique. Metal speciation in the soil solution wasdetermined by a cation exchange resin method. Acetic acid and EDTA extracting solutions were used forextraction of metals in soil solid surfaces. Metal distribution in different fractions of soil solid phase was determined using a three-step sequential extraction scheme. The results show that the metals in the soilsolution existed in different fractions with variable lability and metals in the soil solid phase were also presentin various chemical forms with potentially different bioavail ability and environmental mobility Alkaline-stabilised biosolids could elevate solubility of Cu and proportion of Cu in organically complexed fractionsboth in soil liquid and solid phases, and may therefore increase Cu mobility. In contrast, the biosolids lowered the concentrations of water-soluble Zn (labile fraction) and exchangeable Zn and may hence decrease bioavailability and mobility of Zn. However, Fe and Mn oxides bound and organic matter bound fractions are likely to be Zn pools in the sludge-amended soil. These consequences possibly result from the liming effect and metal speciation of the sludge product and the difference in the chemistry between the metals in soil.  相似文献   

2.
Processes governing the mobilization of Al and Cd in podzols and cambisols of S. Sweden having different tree layer vegetation (Picea abies, Fagus sylvatica, or Betula pendula) were investigated. Speciation of Al and Cd in soil solutions were performed by a column cation exchange procedure (cf. Driscoll, 1984) in combination with thermodynamic calculations. Podzols in spruce and beech stands were characterized by a high release of organic compounds from the O/Ah horizons, resulting in a high organic complexation of Al (c. 93%) in the soil solution from the E horizon (15 cm lysimeters). Organic complexes were mainly adsorbed/precipitated in the upper Bh horizon and the overall transport of Al at 50 cm depth was governed by a pH dependent dissolution of a solid-phase Al pool. In the cambisols, inorganic Al forms were predominant at both 15 and 50 cm depth, and Al solubility was closely related to solution pH. Secondary minerals like synthetic gibbsite, jurbanite, kaolinite or imogolite could generally not explain measured solution Al3+ activities. Results instead indicated that the relatively large organically bound solid-phase Al pools present in both soil types could do so. The column fractionation procedure could be used only qualitatively for Cd, but results strongly indicated that Cd-organo complexes contributed significantly to the overall mobilization of Cd in the podzol E horizons. In all other soil solutions, Cd2+ was the predominant species. Both solid-phase and solution chemistry suggests that ion exchange processes controlled the Cd2+ activities in these solutions. All reactive solidphase Cd was extractable by NH4Cl and Cd2+ activities could in most cases effectively be modeled by the use of ion exchange equations. Solubilized Al3+ efficiently competed for exchange sites and played an important role for the Cd mobilization in these soils.  相似文献   

3.
The soil preference with respect to soil acidity of Asplenium scolopendrium L., Dryopteris filix‐mas (L.) Schott, Pteridium aquilinum (L.) Kuhn as well as of subspecies of the Asplenium trichomanes L. and Polypodium vulgare L. complexes were studied in relation to root cation‐exchange properties. Data were collected for substrate acidity, soil exchangeable cations, and root cation‐exchange capacity. Acidiphilous pteridophytes were characterized by low cation‐exchange capacities. It is unlikely that cation‐exchange properties protect plants from potentially harmful cations such as aluminium or hydrogen, which are abundant under acid soil conditions, through immobilization. It is postulated that cation‐exchange properties are a secondary adaptation to soil acidity, in addition to major adaptations which determine the apparent soil preference. Possibly, a limited variation in cation‐exchange capacity as a function of soil conditions could prevent harmful interactions of soil exchangeable cations with the cation‐exchange sites, such as displacement of cell wall calcium by aluminium or hydrogen ions in acid soils.  相似文献   

4.
Mechanism of reduction of exchangeable aluminum in acid Andosols treated with gypsum was studied by using cation exchange resin methods to determine the amount of polymerized aluminum. Two types of acid Andosols were used as test soils: Kitakami light colored Andosol (fine, mixed, mesic, Andic Dystrochrept) and Kawatabi thick high humic Andosol (medial, mesic mixed Alic Pachic Melanudand). Polymerization of aluminum in the soil solution of both Kitakami and Kawatabi Andosols treated with gypsum was suggested based on an analysis using cation exchange resin methods, whereas that in monomer aluminum solution was not detected. Accumulation of polymerized aluminum in both Kitakami and Kawatabi Andosols was determined by using cation exchange resin, and the amounts of polymer aluminum trapped by the resin and the ratio of polymer aluminum to monomer aluminum were increased with the incubation time. The values of CEC which decreased in the Kitakami Andosol after gypsum treatment were almost equivalent to the amounts of cation exchange sites occupied by polymer aluminum ions which were calculated based on the decrease of the values of Y l. We conclude that the mechanism of reduction of exchangeable aluminum in strongly acid Andosols treated with gypsum is as follows: firstly, exchangeable aluminum adsorbed on the cation exchange sites of soils may be released into the soil solution due to the increase in the ion strength caused by gypsum application, and then monomer aluminum in soil solution may be polymerized in the presence of soil colloidal materials. Consequently, the polymer aluminum formed in the soil solution may be selectively and irreversibly fixed on the cation exchange sites of 2 : 1 clay minerals.  相似文献   

5.
Abstract

Aluminum concentrations in soil solutions are not only controlled by inorganic clay minerals but also by organically bound aluminum. The objective of this study was to determine which pools contribute to Al dissolution. Soil samples were taken at various distances from tree trunks and at various depths at the Rolling Land Laboratory (RLL), Hachioji, Tokyo. Selective dissolution techniques were used to analyze the changes in pools of solid-phase aluminum. Soil pH values around Hinoki cypresses were in the aluminum buffer range. Exchangeable aluminum contents in soils under Hinoki cypresses were 104 mmolc kg-?1 on the average. This value was similar to that of the cation exchange capacity (CEC) of Andisols at RLL at a soil pH of 4. The relationship between the soil pH and exchangeable, organically bound, and amorphous aluminum pools showed that dissolved aluminum ions in the soil solution were primarily derived from the amorphous Al pool. Dissolved aluminum ions were substituted with base cations of soils, resulting in the increase of the content of exchangeable Al and/or the formation of complexes with organic matter which increased the proportion of organically bound Al pools. Increase in the proportion of organically bound Al pools indicated the importance of complexation with soil organic matter for controlling the aluminum concentration in the soil solution.  相似文献   

6.
The discharge of acidic mine drainage waters onto a hillslope in Dalarna, central Sweden, has lead to the contamination of the podzol soils with Cu, Fe, Ni, Pb, Zn and sulfate. Samples from contaminated and reference soils have been collected for chemical and mineralogical analyses. Jarosite is identified by x-ray diffraction analysis as a precipitate in the upper horizons (A, E, B) of the contaminated soils, where the soil acidity (pHKCl~2.6) promotes jarosite stability. The sequential chemical extraction of soil samples indicates that, in the reference A horizon, Cu, Pb, Ni and Zn are bound primarily to cation exchange sites and organic matter. In the A horizon of the contaminated soils closest to the rock dump, metal partitioning is dominated by the Fe oxide fractions, despite the high organic matter content; Pb is almost completely bound to crystalline Fe oxides, possibly adsorbed to Fe oxides or occuring in a jarosite solid solution. In the reference B and C horizons, Cu, Ni and Zn are primarily adsorbed/coprecipitated in the Fe oxide fractions, while Pb remains with a large fraction bound to organic matter. In the Fe-rich B horizon of the contaminated soils, the partitioning of the metals in cation exchange sites and to organic matter has greatly increased relative to the reference soils, resulting from the mobilization of organo-metal complexes down the profile.  相似文献   

7.
The long‐term sustainability of forest soils may be affected by the retention of exchangeable nutrient cations such as Ca2+ and the availability of potentially toxic cations such as Al3+. Many of our current concepts of cation exchange and base cation saturation are largely unchanged since the beginnings of soil chemistry over a century ago. Many of the same methods are still in use even though they were developed in a period when exchangeable aluminium (Al) and variable charge were not generally recognized. These concepts and methods are not easily applicable to acid, highly organic forest soils. The source of charge in these soils is primarily derived from organic matter (OM) but the retention of cations, especially Al species, cannot be described by simple exchange phenomena. In this review, we trace the development of modern cation exchange definitions and procedures, and focus on how these are challenged by recent research on the behaviour of acid forest soils. Although the effective cation exchange capacity (CECe) in an individual forest soil sample can be easily shown to vary with the addition of strong base or acid, it is difficult to find a pH effect in a population of different acid forest soil samples. In the very acidic pH range below ca 4.5, soils will generally have smaller concentrations of adsorbed Al3+. This can be ascribed to a reduced availability of weatherable Al‐containing minerals and a large amount of weak, organic acidity. Base cation saturation calculations in this pH range do not provide a useful metric and, in fact, pH is modelled better if Al3+ is considered to be a base cation. Measurement of exchangeable Al3+ with a neutral salt represents an ill‐defined but repeatable portion of organically complexed Al, affected by the pH of the extractant. Cation exchange in these soils can be modelled if assumptions are made as to the proportion of individual cations that are non‐specifically bound by soil OM. Future research should recognize these challenges and focus on redefining our concepts of cation retention in these important soils.  相似文献   

8.
The addition of biochar to soils appears to be attractive for sequestering carbon and improving soil fertility. Biochar has been shown to alter carbon, nutrient and element cycling, but there is little information on the cycling of trace elements, which will be introduced increasingly into soils because of their use in modern technologies (e.g. rare earth elements) and significant concentrations in phosphate fertilizers. This study investigated, using column experiments, the effect of biochar addition on the leaching of soil‐derived trace metals from a soil contaminated with heavy metals. The biochar used in this study showed a clear potential to reduce soil‐derived trace metals, including transition metals, rare earth elements and heavy metals such as cadmium (Cd) and lead (Pb), while increasing the amounts of essential nutrients such as potassium (K) and molybdenum (Mo). Uranium was mobilized in the presence of biochar, indicating a risk of increased leaching in biochar‐amended soils. During elution under anoxic conditions manganese (Mn) and iron (Fe) oxides were reduced and a release of metals typically bound to these oxides such as Pb, cobalt (Co), zirconium (Zr) and niobium (Nb) was observed. The retention of dissolved organic matter (DOM) in the amended soil led to a retention of DOM‐associated elements such as copper (Cu), zinc (Zn) and nickel (Ni). Analysis by liquid chromatography followed by ICP‐MS indicated an association with UV‐active DOM. In previous studies conducted with inorganic metal species added to soil, an increased retention of metals has often been interpreted as being caused by cation exchange with the biochar. Our results indicate that the decreased mobility of trace elements is at least partly caused by an enhanced retention of metal‐binding DOM after biochar application.  相似文献   

9.
There is an urgent need to improve the methods to estimate solute fluxes in soil, e.g. cumulative capture of leaching ions by exchange resin cores. We compared the suitability of different resin materials, core sizes, and installation procedures to assess nutrient leaching in a highly permeable, tropical Xanthic Ferralsol. Three different cation and anion resins, respectively, and two combined anion-cation resins were tested in laboratory experiments with respect to their removal and recovery of nutrients (Mg, NH4+, NO3) and total dissolved organic carbon (TOC) from solution. In a field experiment, cores with three different diameters (25, 100, and 200 mm) were installed either vertically from the soil surface or laterally from a soil pit. Cumulative leaching of NO3 and NH4+ and of applied Sr was determined after 45 days. The combined anion and cation exchange resin (MB 20) showed satisfactory recovery of NO3 and NH4+ from solution. None of the investigated resins could be used for TOC removal from solution due to high contents of soluble carbon compounds in the resins. Wetting and drying cycles did not affect the removal of solutes from solution or subsequent recovery from the MB 20 resin. Additionally, the combined resin MB 20 was easier to handle than separate anion or cation resins and was therefore used for further field experimentation. The smallest core size (25 mm) was not suitable for nutrient leaching determination due to high preferential flow along the inner core walls. The medium diameter cores (100 mm) showed the lowest variability and the best correlation between NO3 and Sr capture. They were easier to install and retrieve than the large diameter cores (200 mm), which posed serious handling problems and soil disturbance. The lateral installation caused significantly lower artificial flow in comparison to a vertical installation, which was shown by the lower Sr loss and slightly lower N capture. Therefore, a lateral installation of medium sized resin cores (100 mm diameter) from a soil pit was superior to the other alternatives tested in this study.  相似文献   

10.
To examine the possibility that the Al13 polymer ([A104Al12(OH)24(H20)12]7+) could be formed in soils after gypsum application, an analytical method using a cation exchange resin and 27Al nuclear magnetic resonance (NMR) spectroscopy was applied to gypsum-treated Kitakami Andosol (fine, mixed, mesic, Andic Dystrochrept). The NMR spectra of the cation exchange resins which retained artificially synthesized hydroxy-AI, showed two broad peaks at 0 and 63 ppm. These results indicated that monomer and/or dimer Al and Al13 polymers adsorbed on the cation exchange resin could be detected with 27Al NMR. The amount of polymer Al increased by gypsum application in the Kitakami soil. The NMR spectrum of this resin showed only one peak at 0 ppm indicating that the polymer Al formed in the gypsum treated Kitakami soil was not the Al13 polymer.  相似文献   

11.
Profiles of arid and semi‐arid zones soils of Punjab, northwestern India, were investigated for different forms of iron (Fe): total Fe, diethylenetriamine penta‐acetic acid (DTPA)–extractable Fe, soil solution plus exchangeable Fe, Fe adsorbed onto inorganic sites and oxide surfaces, and Fe bound by organic sites. Irrespective of the different fractions of Fe present, its content was higher in the fine‐textured Alfisols and Inceptisols than in the coarse‐textured Entisols and Aridisols. Lower content of total Fe was observed in the surface horizon and then increased in the subsurface horizons, whereas no set pattern was observed in Entisols. Also, irrespective of the soil orders, the contents of different forms of Fe were higher in the surface horizon and then decreased by depth. None of the forms of Fe exhibited any consistent pattern of distribution.

Organic matter and the content of clay and silt fractions had a strong bearing on the distribution of forms of Fe. Based on a linear coefficient of correlation, the soil solution plus exchangeable Fe adsorbed onto inorganic sites and DTPA‐extractable Fe increased with increase in soil organic carbon but decreased with increase in soil pH and calcium carbonate content. Total Fe increased with increase in cation exchange capacity (CEC) and clay and silt content. The results also revealed that there was equilibrium in different fractions of this element. Among the different Fe forms, Fe bound by organic sites, water‐soluble plus exchangeable Fe, and Fe adsorbed onto oxides (amorphous surfaces) were positively correlated with the DTPA‐extractable Fe. Though some forms are interrelated, none of the forms had any relationship with the total Fe.  相似文献   

12.
The interactions between the adsorption characteristics of 27 experimental soils and the sorption of Cd and Ni from the municipal wastewaters were investigated in this study. The removal of these elements from soil solution was followed for 50 days. All the adsorption characteristics, except cation exchange capacity and organic matter, were significantly correlated to the sorption of Cd after one day shaking. After 7 days of shaking, none of the soil adsorption characteristics except free CaCO3 was significantly correlated to Cd removal from wastewater. The soil saturated paste pH and suspension pH were strongly correlated to Cd sorption throughout this experiment. The behavior of Ni in soils was different from that of Cd. Surface area, total Fe, and total Al were significantly correlated to Ni sorption. The correlation between Ni removal and pH was the strongest than any other parameter studied. After 7 days shaking, clay content and total Ca were not significantly correlated to Ni sorption. The cation exchange capacity of the soils was not significantly correlated to Cd or Ni sorption in this experiment. It seems that in the experimental soils, concentration of Cd and Ni were probably not controlled by adsorption process. The precipitation process was probably playing a major role in the removal of these elements from the municipal wastewaters. As observed in this experiment, the cation exchange capacity of experimental soils was a poor parameter to define sorption capacity of these soils for Cd and Ni. The guidelines for determining the soil sludge load, which are mainly based on the cation exchange capacity of soils, should be revised.  相似文献   

13.
Soil humus plays a significant role in the cation exchange of a soil. YOSHIDA (1) showed that, as a general rule, divalent ions such as calcium and magnesium were adsorbed more strongly onto humus than monovalent ions such as ammonium and potassium in an ion-exchange reaction. He did not, however, describe the behavior of heavy metal ions. BREMNER et al. (2) first suggested that soil organic matter forms complexes with polyvalent cations. HIMES and BARBER (3) found that soil organic matter reacts with divalent metal ions in a manner similar to the chelation reaction. Reviews of the soil organic matter-metal complex have been written by BREMNER et al. (2) and KAWAGUCHI, MATSUO and KYUMA (4).  相似文献   

14.
Phosphorus (P) adsorbed by iron (Fe) oxyhydroxides in soil can be released when the Fe(III) minerals are reductively dissolved after soil flooding. However, this release is limited in tropical soils with large Fe contents and previous studies have suggested that P sorbs or precipitates with newly formed Fe(II) minerals. This hypothesis is tested here by scavenging Fe2+ in flooded soils by increasing the cation exchange capacity (CEC) of soil through resin application (30 cmolc kg?1; Na‐form). Three soils from rice paddies with contrasting properties were incubated in aerobic and anaerobic conditions with or without resin and with or without addition of organic matter (OM) to stimulate redox reactions. Dissolved Fe was 0.1–1.1 mm in unamended anaerobic soils and decreased to less than 0.07 mm with resin addition. Anaerobic soils without resin and aerobic soils with or without resin had marginal available P concentrations (<2 mg P kg?1; anion‐exchange membrane P). In contrast, available P increased 3‐ to 14‐fold in anaerobic soils treated with resins, reaching 16 mg P kg?1 in combination with extra OM. Application of Ca‐forms of resin did not stimulate P availability and dissolved Ca concentrations were larger than in unamended soils. Resin addition can increase P availability, probably by a combination of reducing solution Fe2+ (thereby limiting the formation of Fe(II) minerals) and increasing the OM solubility and availability through reducing dissolved Ca2+. The soil CEC is a factor controlling the net P release in submerged soils.  相似文献   

15.
Phosphate extracted by ion-exchange resins in the chloride and sodium forms from a deep river-gravel soil under widely varying conditions is always from the isotopically exchangeable or‘labile’ pool. At any reaction time, a constant fraction of this pool is desorbed by the chloride form of the anion-exchange resin alone, irrespective of the pH and phosphate manuring of the soil. If, however, a sodium: cation exchange resin is included, increasing fractions of the‘labile pool’ are desorbed with decreasing soil acidity. Phosphate desorption by the anion-exchange resin alone and with the cation exchange resin is shown to be‘particle-diffusion’ controlled in the anion exchange resin and neither a‘chemical reaction’ nor a‘film-diffusion’ mechanism. Over the pH range 4·5–8·5, values between 4·8 and 0·9 × 10-9 cm2 sec-1 were calculated for the interdiffusion coefficient of the phosphate: chloride exchange process in the resin. The isotopically exchangeable phosphate in the soils seems to behave like sparingly soluble or weakly dissociating compounds towards ion-exchange resins and its rate of desorption depends on the nature and composition of the resins.  相似文献   

16.
Long-term acidification has been shown to result in a considerable decrease in the amount of organically bound soil Al and in a gradual decrease in the solubility of Al. We examined the solubility of soil organic matter (SOM) and Al in four acid mineral soils (one Arenosol Ah, two Podzol Bh, and one Podzol Bs) as they were leached sequentially using a solution containing 0.001 m HCl and 0.01 m KCl. The acid leaching resulted in relative decreases in Al that were 2–6 times greater than for organic C. The organic C and Al dissolved by the acid leaching originated mainly in the pyrophosphate-extractable fraction of the elements. Protonation seems to be a major mechanism in stabilizing the residual SOM, as indicated by small changes in effective cation exchange capacity with the degree of acid leaching. In the samples of Podzol Bh and Arenosol Ah soils the solubility of Al (defined as log10{Al3+} + 1.5pH) in equilibrium suspensions (0.01 m KCl) was closely related to the ratio of pyrophosphate-extractable Al to pyrophosphate-extractable organic C. The Podzol Bs sample probably contained a small amount of a surface-reactive Al(OH)3 phase, which rapidly became depleted by the acid leaching.  相似文献   

17.
A humic lake of pH 5.6 was acidified with H2SO4 to pH 4.1. Measurements of total and hollow-fiber ultrafiltered samples were made after three different times of storage, before and after the acid treatment. The nominal molecular weight cutoff of the hollow-fiber membrane was 10 kDalton. Assuming a linear molecular weight distribution of the organic complexes present in solution, the average organic molecule had an average molecular weight of 12.8?08 kDalton (n=6). Not only Ca2+ and Mg2+, but also detectable amounts of Na+ and K+ was found to be present on high molecular weight forms. No significant change in the molecular weight distribution of these elements were observed after the pH decrease. Changes in the molecular weight distribution after the acid treatment were only observed for Fe and Al. Significant amounts of SO4 2? were present on high molecular weight forms. A small, but significant increase in the relative amounts of SO4 2? present on high molecular weight forms was observed after the pH lowering. Kinetic constraints were demonstrated for dissolution of Al and Fe. To some extent, kinetic constraints in the equilibrium distribution of cation/anion exchange reactions of Al, Fe, and SO4 2? were also observed. After the acid treatment, the cation exchange capacity (CEC) of the organic pool present was estimated to be at least 18.2±1.4 (n=3) μeq of positive charges per mg C, probably because the negative sites on the organic pool are either not totally protonated or occupied by other cations at pH 4.09. This CEC is of the same order as industrially made cation exchange resins.  相似文献   

18.
酸化及施碳酸钙对土壤各形态锰的影响   总被引:7,自引:1,他引:7  
以灰潮土为对照 ,研究了华中地区 3种已明显发生酸化的土壤在施用碳酸钙前后各形态锰的变化情况。结果表明 ,已酸化的红壤、棕红壤和黄褐土施用碳酸钙降低了土壤酸度 ,土壤交换态锰随 pH值上升而降低 ,其降幅分别为 42 % ,49%和 39% ;其它形态锰的增减随各土而异 ,残留态锰较稳定 ,变幅小。作为对照 ,灰潮土虽与前 3种已酸化土壤一样种植过多茬作物 ,但其交换态锰含量仍甚微。无论是否施用碳酸钙 ,在灰潮土的交换态锰、碳酸钙结合态锰和易还原态锰 3种形态锰中 ,易还原态锰占 80 %以上 ,说明易还原态锰是其活性锰的主要部分  相似文献   

19.
The buffering of protons and hydroxyl ions in acid soils was studied by the addition of small amounts of HCl, H2SO4, and NaOH in consecutive batch experiments using surface soils and subsoils from two Cambisols and one Podzol. A chemical equilibrium model was used to study the main buffer processes. The model included inorganic complexation and multiple cation exchange, and also the solubility of jurbanite and Al(OH)3 for the subsoils. Buffering of protons was predicted quite well by the model for the surface soil of the Spodi-Dystric and Spodic Cambisols, suggesting that multiple cation exchange was the main buffer process. For the Podzol surface soil, however, the model overestimated proton buffering by cation exchange considerably. Hydroxyl buffering in acid surface soils could be described well by the model for the Podzol soil only. For the Cambisols, hydroxyl buffer reactions included not only cation exchange, but also solubilization of large amounts of organic matter and presumably deprotonation of dissolved organic carbon (DOC). Modelling proton and hydroxyl buffering in subsoils suggested that equilibrium with AJ(OH)3 was not maintained for the Podzol and spodic Cambisol. Sulphate sorption had to be considered to describe titration experiments in all three soils. The assumption of jurbanite being in equilibrium with soil extracts was useful only for the Spodi-Dystric Cambisol.  相似文献   

20.
Abstract

Zinc fractions occurring in five wetland soils as a function of organic matter application and soil redox potential were studied under laboratory conditions. The results indicate that a large portion of native or added Zn is bound to the soil mineral component. Exchangeable and organic complexed Zn and Zn bound to amorphous and crystalline sesquioxides were found to be in dynamic equilibrium. Exchangeable and complexed Zn were positively correlated with both native and/or added organic matter, while Zn bound to the amorphous and crystalline sesquioxides were negatively correlated with added organic matter. As soil redox potential decreased, the amount of exchangeable and organic complexed Zn decreased, while Zn bound to the amorphous and crystalline sesquioxides increased. Zinc fractions examined varied, depending upon soil cation exchange capacity, clay and organic carbon content.  相似文献   

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