Enhanced sorption and fixation of radiocaesium in soils amended with K-bentonites, submitted to wetting–drying cycles

The use of bentonites as soil amendment has met with little success in reducing plant uptake of radiocaesium. However, bentonites exchanged with K⁺ have pronounced Cs⁺ binding capacity when subjected to wetting–drying cycles. Fifty‐four different bentonites were collected and characterized for cation exchange capacity and chemical composition. The radiocaesium interception potential (RIP) increased up to 160‐fold (mean 25) when the bentonites were converted to the K‐form and subjected to wetting–drying cycles. This increase in radiocaesium sorption was ascribed to a collapse of the clay sheets into an illite‐like structure, and was most pronounced in bentonites with a high layer charge. The RIP values of K‐bentonites subjected to 25 wetting–drying cycles ranged from 0.22 to 44.3 mol kg^?1. The RIP yields, i.e. the RIP in soil–bentonite mixtures expressed per unit bentonite added, were even higher and ranged up to 99 mol kg^?1. This upper limit is about 10‐fold higher than the RIP value of illite (～ 10 mol kg^?1), the principal ¹³⁷Cs sorbent in soils of temperate climates. Wetting–drying also promoted fixation of radiocaesium in soils amended with K‐bentonites. About 30% of added ¹³⁷Cs could be desorbed with 1 m ammonium acetate (NH₄Ac) from an unamended soil after 25 wetting–drying cycles, while only between 8 and 21% of ¹³⁷Cs could be desorbed from a soil amended with bentonite and a K‐salt. These findings support the proposition that addition of K‐bentonite may be effective in reducing availability of ¹³⁷Cs in soils.     

Potassium bentonites reduce radiocaesium availability to plants

After the Chernobyl accident in 1986 the fate of radiocaesium from the fallout became of pressing concern. Specific soil amendments, as K fertilizer and specific clay minerals, promised to mitigate the worst effects. We therefore investigated the influence of bentonite and the K status of the soil on the radiocaesium equilibria in soil and on its availability to ryegrass. A sample of a sandy soil was contaminated with ¹³⁴Cs and amended with K and Ca salts (0–0.97 mmol kg^?1) and K bentonite (0–2%). After 4 weeks' incubation of the soil mixtures, ryegrass was grown for 18 weeks in a pot trial and harvested on seven occasions. No significant treatment effects on ¹³⁴Cs activity concentrations were found at the first and second harvest. From the third harvest onwards, however, ¹³⁴Cs activity concentrations in the grass were reduced up to twofold (P < 0.05) by increasing rates of K bentonite. Adsorption studies with ¹³⁷Cs revealed that the radiocaesium interception potential (RIP) of the soil–bentonite mixtures (> 1% bentonite) increased about 10‐fold during plant growth. The RIP of the K bentonite after plant growth was up to 10 times larger than that of pure illite. The formation of specific Cs sorption sites is ascribed to the in situ illitization of the K bentonite. The increase in RIP during plant growth is reflected in a decrease in exchangeable K⁺ at 2% K bentonite of about 18%. Radiocaesium concentrations in grass could be reliably predicted from the Cs⁺ and K⁺ concentrations in the soil solution. Adding K bentonite to a soil contaminated with radiocaesium is effective in fixing Cs in the soil.     

Soil acidification under long-term tobacco plantation results in alterations of mineralogical properties in an Alisol

In the present study, soil samples collected from 20-year (1993?2013) long-term tobacco plantation and perennial fallow were analyzed to study the influence of soil acidification on soil physicochemical and mineralogical properties. Results showed a significant decrease of soil pH, Ca²⁺, Mg²⁺, Na⁺ and total exchangeable cations, except K⁺, under tobacco plantation than under fallow land. Further X-ray diffraction (XRD) analysis for 1 mm soil size demonstrated an increase of vermiculite and kaolinite, but an obvious decrease of original potassium-bearing mica and potassium feldspar, under tobacco plantation than under fallow. For the <2 μm soil clay fraction, the XRD patterns showed an obvious desilication and accumulation of Al and Fe under tobacco plantation than under fallow. Other potassium-bearing minerals, such as illite and chlorite, had also visibly weathered and slaked under tobacco plantation than under fallow, resulting in an increase of vermiculite and hydroxy-Al-vermiculite, and an accelerated decomposition of 2:1 minerals and formation of 1:1 minerals. These results demonstrated that long-term continuous tobacco plantation has exerted negative effects on soil acidification and maintenance of soil potassium-bearing minerals.     

Effect of residence time on the kinetics of nonexchangeable ammonium release from illite and vermiculite

The fraction of nonexchangeable ammonium (NH₄⁺) can play an important role in N cycling of soils as a sink (fixation) or a source (release) of NH₄⁺. Recently fixed nonexchangeable NH₄⁺ especially seems to be a significant source for N release. The aim of our study was to determine the effect of residence time on the kinetics of nonexchangeable NH₄⁺ release from illite and vermiculite. Calcium-saturated illite and vermiculite, containing NH₄⁺ that was “fixed” for one and 60 d, were extracted with a H-resin for 0.25 to 384 h. Both clay minerals “fixed” significantly more NH₄⁺ in 60 d than in 1 d, but vermiculite “fixed” more NH₄⁺ than illite. The kinetics of nonexchangeable NH₄⁺ release from illite and vermiculite were well described by the Elovich equation and by a heterogeneous diffusion model. In vermiculite the percentage of nonexchangeable NH₄⁺ release decreased from 84% to 78% when the time of fixation increased from 1 to 60 d. In illite time of residence has not influenced the complete release of newly fixed NH₄⁺.     

Effect of 137Cs accumulation by organomineral coarse particles in sandy soils contaminated during the Chernobyl NPP accident

Dark-colored particles in the coarse fractions of sandy soils were found to concentrate ¹³⁷Cs. Up to 94% of the fractional ¹³⁷Cs was associated with these particles in the sand and coarse silt fractions, although their relative mass did not exceed 1–5%. The concentrations of ¹³⁷Cs in the dark-colored particles were up to 400 times higher than those in the light-colored particles. The high values of the radiocesium interception potential (RIP(K) = 1600–4600 mM/kg) indicate the presence of clay minerals in the dark particles.     

Bilanzierung der Tonbildung und -verlagerung sowie der Tonmineralumwandlung in Löß-Parabraunerden

Balances of alteration and migration of clay fractions and clay minerals in Gray Brown Podzolic Soils from Loess Balances of alteration and migration of clay fractions, clay minerals, K, Mg and Fe bound in clay silicates were calculated for Gray Brown Podzolic Soils (Parabraunerden) derived from Young Pleistocene Loess below arable and forest land in the district south of Würzburg. The extent of clay formation lies between 63 and 98 kg/m², of which 60–80 % belong to the fraction <0.1 μm. The clay migration varies between 35 and 51 kg/m², the fractions < 0.2 μm (especially the fraction <0.1 μm) predominating, the coarse clay being involved only to a smaller extent. During Holocene soil formation 121 kg illite, 16 kg vermiculite and 11 kg kaolinite per m² are formed in the clay fraction (< 2 pm). The loss of smectite amounts to 68 kg/m². The biggest alterations of the clay mineral quantities occur in the fraction <0.1 pm; they indicate a smectite-illite transformation. Illite, at 23 kg/m², accounts for half of the clay migration, followed by smectite and vermiculite each at 9 kg/m² and kaolinite at 5 kg/m². When comparing the migrated with the present amounts no preference of certain clay minerals during clay migration can be determined. In the clay fractions the gained Fe (3.07?4.32 kg/m²) and K (2.75?3.84 kg/m²) predominate over Mg (0.57?1.15 kg/m²). The three elements accumulate to the greatest extent in the fine clay fraction. The element migration parallels the gain. The balances of the elements are discussed in connection with pedogenic illite formation as well as biotite and vermiculite disintegration.     

The forms and availability to plants of soil potassium as related to mineralogy for upland Oxisols and Ultisols from Thailand

Potassium (K) deficiency is widespread in crops on highly weathered upland soils under a tropical monsoonal climate. Critical assessment of the forms of K in soils and of the ability of soils to release K for plant uptake is important for the proper management of K in crop production. The relationships between different pools of K were investigated as a function of silt and clay mineralogy for 14 upland Oxisols and 26 upland Ultisols soils from Thailand. Most soils contained no K-minerals in the silt fraction. XRD showed that kaolinite is the dominant clay mineral with variously minor or moderate amounts of illite, hydroxy-Al interlayered vermiculite and smectite present in some soils. For some soils, both conventional and synchrotron XRD were unable to detect illite. Analytical TEM including EFTEM of individual clay crystals showed that clay in the apparently illite-free samples contained very small amounts of illite. Many kaolinite particles appear to contain K which may be present in illite interleaved with kaolinite crystals. A glasshouse K-depletion experiment was conducted to assess the K supply capacity and changes in chemical forms of K and K-minerals using exhaustive K depletion by Guinea grass (Panicum maximum). Potassium deficiency symptoms and mortality of plants occurred on light textured soils, whereas plants survived for six harvests for Oxisols with clay texture, relatively high CEC and higher NH₄OAc-K (exchangeable K plus water-soluble K). There is a strong linear relationship of unit slope between NH₄OAc-K and cumulative K uptake by plants indicating that NH₄OAc-K is a major form of K available to plants. Thus K-bearing minerals contributed little K to plants over the time scale of the experiment and XRD patterns of whole soil samples, silt and clay from soils after cropping mostly showed no change from those for the initial soil. An exception was for a single surface soil clay where a minor amount of smectite was formed from illite by K release to plants.     

Fixation of radiocaesium in an acid brown forest soil

The OAh and Ah horizons of acid brown and podzolic forest soils are reported to fix more radiocaesium than the mineral B horizons beneath them. We determined the respective influence of organic matter and clay minerals on the magnitude of Cs⁺ retention in a strongly acid brown forest soil in Belgium. The soil contained mica throughout the profile. Vermiculite was identified in the OAh and Ah horizons, and hydroxy interlayered vermiculite (HIV) in the Bw horizon. The OAh and Ah clay fraction retained much more Cs⁺ than the Bw horizon. The extraction of Al interlayers by Na-citrate resulted in a marked increase in Cs⁺ fixation in the Bw clays as well as the collapse of the vermiculitic layers after K⁺ saturation. Organic matter had a strong but indirect effect on Cs⁺ fixation. In the Bw horizon, acid weathering of layer silicates releases free Al and produces HIV minerals in which Al polymers block the access of radiocaesium onto Cs⁺-specific sites. In OAh and Ah horizons, free Al is complexed by organic acids. Consequently, the interlayer specific sites remain accessible for Cs⁺ fixation.     

Short‐time clay‐mineral evolution in a soil chronosequence in Oléron Island (France)

Major weathering sequences in soils are well established; however, knowledge on rates of mineral transformations remains unknown, because it is often difficult to date precisely soil processes. This work was carried out on soils developed on recent (< 188 y) sand dunes on the W coast of Oléron Island (France). The coast has been protected against marine and wind erosion by constructing five consecutives barriers close to the coastline since 1820 (1820, 1864, 1876, 1889, 1948) defining the maximum age of the soil parent material, as before the areas between the barriers were under water. Soils on the older dunes have low clay content (> 94% of sand) and exhibit a bleached E horizon that overlies a yellowish brown B horizon. The process responsible for their formation is podzolization promoted by the high permeability of the material and complexing organic matter produced by coniferous vegetation. Initial mineralogy of C horizons is homogenous and constituted of chlorite, illite, illite/smectite mixed‐layer minerals, and kaolinite, quartz, calcite (≈ 8% related to shell fragments), and feldspars. The initial clay‐mineral assemblage of the E horizons is dominated by illite (well‐crystallized WCI and poorly crystallized PCI) and chlorite. With progressive podzolization, poorly crystallized illite is first transformed to illite/smectite mixed‐layer minerals and in a further step into smectite. In addition, transformation of well‐crystallized illite leads to formation of ordered illite/smectite mixed‐layer minerals in the E horizons, which is not commonly described in soils. In the B horizons, illite/smectite mixed‐layer minerals are present with traces of smectite, as well as Al and Fe oxi‐hydroxides as revealed by DCB and oxalate chemical extractions. This chronosequence illustrates that over short distances and short time (< 188 y) intense mineral weathering and soil development occur. Major clay‐mineral changes occur between 132 and 188 y in agreement with development of the pine forest producing acidic litter.     

Clay minerals in a soil chronosequence derived from basalt on Hainan Island, China and its implication for pedogenesis

A soil chronosequence consisting of six profiles formed on quartz tholeiite basalt ranging in age from 10,000 years to 1. 8 Million years (My) was studied here. Soil clays were identified using XRD diffractogram decomposition methods for samples obtained from the A and C horizons of profiles. The results showed that kaolinite minerals dominated in all the clay fractions. Gibbsite was prominent in the C horizons in the soils from older rocks. Clays in the A horizon of relatively young soils showed an initial stage of illite formation, followed by smectite mixed layer minerals (illite-smectites and then vermiculite-illite) and finally by vermiculite. The initial presence of illite is interesting as there is no magmatic micaceous or phyllosilicate phase in these basalts and the formation of illite we attribute to a secondary process, probably created by alkali transport by plant materials. The change in 2:1 clay mineralogy reflects the overall change in Si/Al ratios in the soils over longer periods of weathering. In all cases gibbsite is more abundant in the C horizons than the A horizons. The difference in gibbsite content between the A and C horizons we attribute to plant transport of siliceous phytolite material to the surface. Continued high rainfall over long periods of time removed the alkali faster than the plants could bring it to the surface, which led to continuous lowering of 2:1 minerals from younger to older in the soil chronosequence. Nevertheless a 2:1, silica-rich mineral persists in the clay assemblages although in very minor amounts.     

Use of soil nonexchangeable potassium by paddy rice with clay structural changes under long-term fertilizer management

To prove the hypothesis that paddy rice utilizes soil nonexchangeable potassium (neK) and causes associated structural changes in clay minerals, K status and clay mineralogy of 22 surface soils from three paddy fields under long-term fertilizer management for 51–93 years were investigated. Soil neK content was determined as the difference between 1 mol L⁻¹ hot HNO₃ extractable K and 1 mol L⁻¹ ammonium acetate exchangeable K. Clay mineralogy was identified by X-ray diffraction (XRD). The radiocesium interception potential (RIP), an index of frayed edge sites in the interlayer sites of 2:1 type clay minerals, was also determined. The neK contents under the -K and NPK treatments were considerably lower than those under the unfertilized treatment in all the fields, indicating the exploitation of soil neK by rice. XRD analysis of the clay samples revealed 7% shift from the 1.0 peak to 1.4 nm one under the -K treatment compared with the unfertilized one, and the amounts of neK were negatively correlated with those of RIP (p < .01), suggesting the expansion of interlayer spaces of the 2:1 type phyllosilicates such as mica due to the release of neK. In addition, the neK content positively correlated with K balance of the long-term experiments (p < .05). The differences of neK between unfertilized K and -K treatments corresponded to 22–157 kg K ha⁻¹, or 0.42–1.68 kg K ha⁻¹ year⁻¹. In conclusion, utilization of considerable amount of soil neK under K depleted conditions should be considered to establish sustainable K management for paddy rice.     

皖南第四纪红土伊利石结晶度值与风化强度的关系

对安徽宣城市宣州和郎溪两地第四纪红土黏土矿物组合和伊利石结晶度进行研究,探讨其对第四纪红土形成环境的指示意义。结果表明,两地第四纪红土黏土矿物的组合基本相似:剖面上部末次冰期下蜀黄土层(黄棕色土层)黏土矿物主要为伊利石、高岭石和2∶1型的蛭石;均质红土和网纹红土以伊利石和高岭石为主,无蛭石;网纹层下部出现伊利石-蒙脱石混层矿物。根据伊利石的X射线衍射(XRD)峰,获得伊利石结晶度(Illite crystallinity,IC)值,可以反映伊利石结晶程度。两地第四纪红土同类层次的IC值较接近。宣州和郎溪剖面黄棕色土的IC值平均为0.463,均质红土为0.599,网纹红土为0.726。全剖面样品IC值与风化强度指标呈显著负相关,充分说明红土IC值可有效地反映红土的风化强度。第四纪红土剖面从黄棕色土→均质红土→网纹红土,IC值升高,伊利石结晶变差,反映了红土风化强度增加,形成的气候环境更加湿热。     

A Merging Algorithm for Aerosol Size Distribution from Multiple Instruments

The work focuses on application of linear regression method for assessment of soil physicochemical parameters influence on ¹³⁷Cs accumulation. Besides organic matter content and pH, the parameters related to sorption properties of mineral parts and mobile ions concentration were considered. Before linear regression model is applied the data were transformed using Box–Cox formula. Selection of explanatory variables for regression was based on Akaike Information Criterion (AIC). Analysis of residuals distribution showed that linear regression can be applied for assessment of Cs⁺ accumulation in soil horizons. The important conclusion is that Cs⁺ cation migration in soil is usually influenced by more than a single horizon parameter. Common influence of two or more parameters on ¹³⁷Cs activity in soil horizon was observed. Our results suppose that migration of Cs in soil is affected mainly by horizon’s acidity, presence of minerals and ion exchangeable substances. Some processes are probably affected by Cs⁺ individual properties, but other ones are not so selective.     

中国东南部某些水稻土的矿物学

Limited information is available concerning the mineralogy of paddy soils in the southeastern China. Using chemical methods in conjunction with X-ray diffractometry, we studied the mineral composition of three paddy soils: Jinghua (paddy soil on Quaternary red clay), Fuyang (Hapl-percogenic loamy paddy soil), and Shaoxing (gleyic clayey paddy soil). All the soils contained quartz, mica, vermiculite, chlorite and kaolinite, and the distribution of these minerals varied with soil particle size fractions. The clay fraction of the Fuyang and Shaoxing soils also contained smectite. Although X-ray data did not show the presence of smectite in the Jinghua soil, this mineral was identified by the chemical method, suggesting a transitional property of the mineral in the soil. Hydroxy-Al interlayered minerals were also present in the clay fraction. The amount of smectite in the soils was 31.6 (Shaoxing), 16.5 (Fuyang), and 21.4 (Jinghua) g kg^-1; for vermiculite it was 33.3 (Shaoxing), 16.5 (Fuyang), and 8.5 (Jinghua) g kg^-1. Smectite was only found in the clay fraction. In contrast, amounts of vermiculite in soil particle size fractions were 3.0~11.4 (sand), 2.1~6.0 (coarse silt), 4.6~18.9 (medium silt), 0.9~40.0 (fine silt), and 17.0~108 (clay) g kg^-1. The amount of noncrystalline aluminosilicates in the soils in g kg^-1 decreased in the order: Shaoxing (2.4) > Jinghua (1.9) > Fuyang (1.7). This study has provided useful mineralogical information that is fundamental in future development of management strategies of the soils.     

Transformation of clay minerals in nanoparticles of several zonal soils in China

Purpose

Clay minerals significantly affect the physical, chemical, and biological processes of soils. They undergo spontaneous modification and transformation depending to the climatic conditions. Information concerning the compositions and transformation of clay minerals in nanoparticle colloids (NPs) (25–100 nm) is severely lacking. Studying clay mineral transformation is important approach to understand soil formation. This study was conducted to determine the transformation sequence of clay minerals in several zonal soil NPs.

Materials and methods

Four soils (Haplustalf, Alf-1; Hapludalf, Alf-2; Hapludults, Ult-1 and Ult-2) were collected from B horizons developed under three different climatic zones of China. Alf-1 (36° 05′ N and 117° 24′ E) was located under a warm temperate zone and Alf-2 (30° 38′ N and 115° 26′ E), Ult-1 (29° 13′ N and 113° 46′ E), and Ult-2 (19° 27′ N and 109° 17′ E) under a subtropical zone. The clay particles (<?2000 nm) (CPs) and nanoparticles (25–100 nm) (NPs) of tested soils were separated. The element composition of CPs and NPs was identified by microwave digestion method. The mineralogy and chemical bonding of clay minerals were studied by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR).

Results and discussion

With decreasing latitude, NPs and CPs showed that the molar ratio of SiO₂ to Al₂O₃ trends to diminish, indicating the phenomenon of desilication and allitization in the tested soils. XRD analysis revealed that the main clay mineral of Alf-1 NPs was illite, followed by vermiculite, kaolinite, and kaolinite interstratified minerals (KIMs). The clay minerals of Alf-2, Ult-1, and Ult-2 NPs were dominated by kaolinite (and KIMs), followed by illite, with a little content of hydroxyl-interlayered vermiculite (HIV) in Ult-1 NPs and trace content of gibbsite in Ult-2 NPs. With decreasing latitude, vermiculite and HIV decreased in NPs. When compared to CPs, smectite as well as illite-vermiculite mix-layer mineral (I-V) and illite-HIV mix-layer mineral (I-HIV) were not detected in NPs. The analysis of d060 region by XRD showed that with decreasing latitude, the main clay minerals in NPs were dioctahedral minerals (e.g., illite or kaolinite). These clay minerals resulted from the transformation of trioctahedral minerals in CPs. The disappearance of 2:1 swelling minerals and trioctahedral minerals showed that the NPs were more susceptible to weathering than CPs.

Conclusions

With decreasing latitude, the transformation of clay minerals followed the sequence of illite?→?HIV?→?kaolinite?→?gibbsite in tested NPs.

     

Studying the kinetics of <Superscript>137</Superscript>Cs selective sorption by the dynamic method with the measurement of radioactivity in the sorbent solid phase

The dynamic method was proposed for studying the kinetics of ¹³⁷Cs selective sorption by the measurement of the ¹³⁷Cs activity directly in the sorbent solid phase. A thin layer of the sorbent in a disposable syringe membrane filter (MF) was eluted with a ¹³⁷Cs solution containing K⁺ and Ca²⁺ ions with a gradual decrease in the solution flow rate from 6 to 0.2 cm³/min. The activity of the sorbed ¹³⁷Cs was determined periodically by placing the same MF in the detector well of a Wizard 1480 gamma counter. It was shown that the masses of the sorbent and water in the MF had no effect on the efficiency of the ¹³⁷Cs measurement. A linear relationship between the RIP(K) value and the square root of the time for the period between 4 and 30 days was revealed using this method. The relative increase in the RIP(K) with time changed by 6 times (from 0.034 to 0.208 days^−0.5) for the soils and by 20 times (from 0.008 to 0.153 days^−0.5) for the mineral sorbents. The RIP(K) values measured for the interaction of soddy-podzolic soils with ¹³⁷Cs during 24 hours using the standard limited volume method were lower than the values determined by the proposed dynamic method for the interaction period of 30 days by 50–100%.     

K-fixing phyllosilicates in soils: the role of inherited components

K-fixing potential of 29 illite/smectite mixed-layer minerals, covering a broad range in layer ratios and stacking arrangements, has been investigated utilizing X-ray diffraction as the principal investigative tool. Samples were derived from a borehole core transecting Permian sedimentary rocks. In 93% of all samples, K⁺ was retained against replacement with Mg²⁺ from a 1 M MgCI₂ solution in an average of 33% of the smectitic interlayers, defined via expansion to 1.7 nm upon ethylene glycol solvation after Mg-saturation. This non-ideal smectite behaviour points to a vermiculite-type layer charge. Ordered structures fixed on average 20% more K than did random ones, but results were widely scattered. The Greene-Kelly test revealed predominantly tetrahedral substitution, intercalation with dodecylammonium chloride molecules a high interlayer charge density in samples with a high K-fixing capacity. The findings have implications in two fields: in pedology, soils developed from thermally altered sedimentary rocks may inherit a considerable potential for K–fixation; in mineral identification, interlayers in illite/smectite interstratifications fully expanded to 1.7 nm upon ethylene glycol solvation despite their vermiculite–type layer charge. Glycerol solvation provided equally inconsistent results, while dodecylammonium spacings seemed to correlate reasonably well with interlayer charge density characteristics.     

Influence of Aluminum Hydroxide on Potassium Release from Two Colombian Soils

Abstract

The effect of sesquioxides on the mechanisms of chemical reactions that govern the transformation between exchangeable potassium (Kex) and non‐exchangeable K (Knex) was studied on acid tropical soils from Colombia: Caribia with predominantly 2∶1 clay minerals and High Terrace with predominantly 1∶1 clay minerals and sesquioxides. Illite and vermiculite are the main clay minerals in Caribia followed by kaolinite, gibbsite, and plagioclase, and kaolinite is the major clay mineral in High Terrace followed by hydroxyl‐Al interlayered vermiculite, quartz, and pyrophyllite. The soils have 1.8 and 0.5% of K₂O, respectively. They were used either untreated or prepared by adding AlCl₃ and NaOH, which produced aluminum hydroxide. The soils were percolated continuously with 10 mM NH₄OAc at pH 7.0 and 10 mM CaCl₂ at pH 5.8 for 120 h at 6 mL h^?1 to examine the release of Kex and Knex. In the untreated soils, NH₄ ⁺ and Ca²⁺ released the same amounts of Kex from Caribia, whereas NH₄ ⁺ released about twice as much Kex as Ca²⁺ from High Terrace. This study proposes that the small ionic size of NH₄ ⁺ (0.54 nm) enables it to enter more easily into the K sites at the broken edges of the kaolinite where Ca²⁺ (0.96 nm) cannot have access. As expected for a soil dominated by 2∶1 clay minerals, Ca²⁺ caused Knex to be released from Caribia with no release by NH₄ ⁺. No Knex was released by either ion from High Terrace. After treatment with aluminum hydroxide, K release from the exchangeable fraction was reduced in Caribia due to the blocking of the exchange sites but release of Knex was not affected. The treatment increased the amount of Kex released from the High Terrace soil and the release of Knex remained negligible although with Ca²⁺ the distinction between Kex and Knex was unclear. The increase in Kex was attributed to the initially acidic conditions produced by adding AlCl₃ which may have dissolved interlayered aluminum hydroxide from the vermiculite present, thus exposing trapped K as exchangeable K. The subsequent precipitation of aluminum hydroxide when NaOH was added did not interfere with the release of this K, and so was probably formed mostly on the surface of the dominant kaolinite. Measurement of availability of K by standard methods using NH₄ salts could result in overestimates in High Terrace and this may be a more general shortcoming of the methods in kaolinitic soils.     

Distribution and mobility of radiocesium in relation to the clay fraction mineralogy and soil properties in the Iput River floodplain

The role of the mineralogy of the clay fraction and the physicochemical properties of alluvial soils in the floodplain of the Iput River and its tributary the Buldynka River (in the region of the settlement of Starye Bobovichi in Bryansk oblast) in the distribution and immobilization of radioactive isotope ¹³⁷Cs from the atmospheric fallout after the Chernobyl accident was studied. The soils had a sandy texture; a significant variation in the content of amorphous iron oxides (0.1–0.77%) and labile manganese (11.2–193 mg/kg), the cation exchange capacity (6.1–54.2 meq/100 g soil), and the base saturation (29–100%) was common; an appreciable content of X-ray amorphous mineral substances in the clay fraction (<1 μm) enriched with organic carbon (7.7–13.1%); the predominance of trioctahedral hydromicas (Me=50%) in the clay fraction; and the presence of fine-disperse quartz and lepidocrocite. The specific activity of the ¹³⁷Cs in the clay fraction of the moderately and strongly contaminated layers increased with the increasing portion of smectite formations and (or) hydromicas. On the whole, the presence of the clay fraction favored a decrease in the ¹³⁷Cs mobility (the correlation between its content and that of exchangeable cesium was r=?0.608, n=17). However, the portion of exchangeable radiocesium (extracted with 1 M CH₃COONH₄, 1:10) had a tendency toward an increase with increasing content of hydromicas in the clay fraction. Thus, the minerals of this group were a potential source of exchangeable ¹³⁷Cs in the soils. The significant role of amorphous and mobile iron forms in the immobilization and migration of radiocesium in the secondary contaminated horizons of the alluvial soils was revealed.     

水溶性有机碳在各种粘土底土中的吸附：土壤性质的影响

Clay-rich subsoils are added to sandy soils to improve crop yield and increase organic carbon (C) sequestration; however, little is known about the influence of clay subsoil properties on organic C sorption and desorption. Batch sorption experiments were conducted with nine clay subsoils with a range of properties. The clay subsoils were shaken for 16 h at 4 ^oC with water-extractable organic C (WEOC, 1 224 g C L^-1) from mature wheat residue at a soil to extract ratio of 1:10. After removal of the supernatant, the residual pellet was shaken with deionised water to determine organic C desorption. The WEOC sorption was positively correlated with smectite and illite contents, cation exchange capacity (CEC) and total organic C, but negatively correlated with kaolinite content. Desorption of WEOC expressed as a percentage of WEOC sorbed was negatively correlated with smectite and illite contents, CEC, total and exchangeable calcium (Ca) concentrations and clay content, but positively correlated with kaolinite content. The relative importance of these properties varied among soil types. The soils with a high WEOC sorption capacity had medium CEC and their dominant clay minerals were smectite and illite. In contrast, kaolinite was the dominant clay mineral in the soils with a low WEOC sorption capacity and low-to-medium CEC. However, most soils had properties which could increase WEOC sorption as well as those that could decrease WEOC sorption. The relative importance of properties increasing or decreasing WEOC sorption varied with soils. The soils with high desorption had a low total Ca concentration, low-to-medium CEC and low clay content, whereas the soils with low desorption were characterised by medium-to-high CEC and smectite and illite were the dominant clay minerals. We conclude that WEOC sorption and desorption depend not on a single property but rather a combination of several properties of the subsoils in this study.