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Soil organic carbon (SOC), total nitrogen (TN), and total phosphorus (TP) play a vital in plant growth, and their stoichiometric ratios (RCN, RCP, RNP, and RCNP) are important indicators of the elemental balance in the soil ecosystem. However, the effects of land-use change (from natural forest to high-intensity orchards) on dynamics of SOC, TN, TP, and their stoichiometric ratios along the deep soil profile remain poorly understood, especially in the red soil of Southeast China. Therefore, in the present study, we selected the high-intensity managed pomelo orchard systems (7-year-old and 20-year-old) of Pinghe County developed from the natural forest and investigated their soil nutrients distribution and stoichiometric ratios at a depth of 0–200 cm. We found that conversion of natural forest into highly managed pomelo orchard systems effectively increased the SOC (5.01 to 9.05%), TN (98.80 to 126.79%), and TP (507.50 to 1914.65%) contents in the depth of 0–20 cm. On the contrary, in this same depth, RCP and RNP consistently decreased with increasing planting years, while no significant differences were found in RCN between 7-year-old and 20-year-old pomelo orchards. Nonetheless, planting year affected the SOC, TN, RCN, and RCP in the deep soil at 0–200 cm, while TP and RNP at 0–80-cm soil depth. These findings strengthen our understanding of soil nutrients and stoichiometry changes as a result of land-use change and could also provide a vital resource for the evaluation of different land uses.

This study aimed to investigate the mechanism of lead (Pb) immobilization by hydroxyapatite (HAP) in a soil-rice system, a pot experiment was conducted using Pb-contaminated soil amended with various rates of HAP and planted with rice (Oryza sativa L.). The Pb species in the soil and rice roots were determined using Pb L3-edge X-ray absorption near edge structure (XANES). Application of HAP increased soil pH and induced the dissolution of phosphate, subsequently promoting the formation of chloropyromorphite, an insoluble Pb species, in the soil. Therefore, the acid soluble and DTPA-extractable Pb concentrations decreased significantly with increasing levels of applied HAP. HAP reduced the retention of Pb in the iron plaque on the root surface at maturity, thereby alleviating Pb uptake by rice roots. The amount of phosphate in roots were increased with increasing rate of application of HAP, but was negatively correlated with Pb in rice stems and leaves. Application of 32 g kg−1 of HAP triggered the precipitation of Pb5PO4Cl in roots, limiting Pb translocation from roots to shoots. In addition, HAP may induce the redistribution of Pb in rice nodes, lowering the transfer factor of Pb from the stem (or leaf) to rice grains. When the rate of application of HAP exceeds 4 g kg−1, the Pb concentration in brown rice could be reduced to less than the Chinese National Standard of 0.2 mg kg−1 (GB2762-2017).

General acid washing is commonly used to treat heavy metal-contaminated soils, but it is sometimes difficult to achieve remediation aims in severely polluted soils. If we expose the surfaces of Fe oxide minerals to reductive dissolution during washing treatment, more of the metals initially adsorbed to these surfaces will be liberated, which may encourage the removal of heavy metals. Initially, the metal extraction capabilities of nine chemical reductants were compared in ten soil samples polluted by Cr, Cu, Zn, and Ni. Sodium dithionite (Na2S2O4) and ferrous sulfate (FeSO4) were screened for subsequent intensive research. In summary, the Na2S2O4 solutions had higher Cr, Cu, and Zn removal rates than either the FeSO4 or acid solution. Application of dissolved organic carbon (DOC) further increased the removal of heavy metals by complexation. About 15%, 86%, 32%, and 52% of the Cr, Cu, Zn, and Ni, respectively, were removed from the representative soil (M-2) by two-stage washing using 0.2 M Na2S2O4 coupled with 1,500 mg L−1 DOC solution at pH 2.0. Meanwhile, most soil fertility was preserved: ammonium nitrogen was increased 3.9 times; the increase in exchangeable potassium was 33%; and the reduction in available P was only 10%.

This study aimed to determine the microbial diversity at different soil depths (0-5 and 5-20 cm) in a subtropical orchard during different seasons (i.e., spring, summer and autumn) to advance knowledge of the roles of microbes in orchard ecosystem balance. In tracking experiments conducted in an orchard (established in 1996), the phospholipid fatty acid (PLFA) biomarker method was employed to determine the soil microbial system. The total PLFA concentration did not vary significantly between soil depths but changed between seasons. It peaked in the summer at 258.97 ± 23.48 μg g soil-1 from 0-5 cm and at 270.99 ± 58.94 μg g soil-1 from 5-20 cm. A total of 33 microbial fatty acid biomarkers were observed and identified in the sampled soil. The quantities of PLFAs for 29 microbial groups varied significantly between seasons, except for 15:0 iso 3OH, 15:1 iso G, 16:0 2OH, and 17:0 iso 3OH. The bacterial PLFAs and fungal and actinomycetic PLFAs in the orchard soil collected in summer were significantly more abundant than those collected in the spring or autumn (P < 0.01). The number of soil microorganism species (richness) and the Simpson and Shannon-Wiener indexes were all highest in summer. The total PLFAs, bacterial PLFAs, fungal PLFAs, actinomycetic PLFAs, richness, and Simpson and Shannon-Wiener indexes were all significantly negatively correlated with soil pH, total organic carbon (TOC), total nitrogen (TN) and the cation exchange capacity (CEC) (P < 0.05).

This study focused on the effects and mechanisms of biochar amendment to Cd-contaminated soil on the uptake and translocation of Cd by rice under flooding conditions. Pot and batch experiments were conducted using Cd-contaminated soil collected from a field near an ore mining area and a cultivar of Oryza sativa ssp. indica. Biochar derived from rice straw under anaerobic conditions at 500 °C for 2 h was mixed with the soil at the rate of 0, 2.5, and 5%. The application of 5% biochar reduced CaCl2-extractable soil Cd by 34% but increased Cd concentration in brown rice by 451%. Biochar amendment decreased water-soluble Fe2+ in soils and formation of Fe plaques on roots and weakened the Fe2+-Cd2+ competition at adsorption sites on the root surface. Biochar increased water-soluble Cd in the soil and consequently Cd uptake by rice roots by releasing water-soluble Cl−. Biochar application also reduced the proportion of cell wall-bound Cd in the root, which caused easier Cd translocation from the cortex to the stele in the root and up to the shoot. Rice straw biochar (with high concentration of water-soluble Cl−) reduced CaCl2-extractable soil Cd but increased Cd concentration in rice under flooding condition.

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. 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 (

Inappropriate treatments for the effluents from semiconductor plants might cause the releases and wide distributions of selenium (Se) into the ecosystems. In this study, Al/Si and Fe/Si coprecipitates were selected as model adsorbents as they often formed during the wastewater coagulation process, and the removal efficiency of selenite (SeO3) and selenate (SeO4) onto the coprecipitates were systematically examined. The removal efficiency of SeO3 and SeO4 was highly related to surface properties of Al/Si and Fe/Si coprecipitates. The surface-attached Al shell of Al/Si coprecipitates shielded a portion of negative charges from the core SiO2, resulting in a higher point of zero charge than that of Fe/Si coprecipitates. Thus, adsorption of SeO3/SeO4 was favorable on the Al/Si coprecipitates. Adsorptions of both SeO3 and SeO4 on Al/Si coprecipitates were exothermic reactions. On Fe/Si coprecipitates, while SeO3 adsorption also showed the exothermic behavior, SeO4 adsorption occurred as an endothermic reaction. The kinetic adsorption data of SeO3/SeO4 on Al/Si and Fe/Si coprecipitates were described well by the pseudo-second-order kinetic model. SeO4 and SeO3 adsorption on Fe/Si or Al/Si were greatly inhibited by the strong PO4 ligand, whereas the weak ligand such as SO4 only significantly affected SeO4 adsorption. The weakest complex between SeO4 and Al was implied by the essentially SeO4 desorption as SeO4/PO4 molar ratios decreased from 0.5 to 0.2. These results were further confirmed by the less SeO4 desorption (41%) from Fe/Si coprecipitates than that from Al/Si coprecipitates (78%) while PO4 was added sequentially.

Information on phosphorus (P) adsorption and its impacts on the redistribution of the P fraction in soil profiles are important for environmental management under intensive agricultural practices. To clarify the dominant factors influencing soil phosphorus adsorption in an Entisol (locally known as purple soil), P adsorption experiments were conducted in Sichuan Basin of southwestern China for cropland and woodland soils with acidic, neutral and calcareous origins throughout their profile. After various doses of P were added during incubation experiments, soil P fractions were also analyzed. The results showed that there were no significant differences in Fe-oxides and P adsorption along the vertical gradients. Agricultural practices and lower pH conditions reduced the P adsorption capacity of purple soils throughout the soil profiles. For acidic and neutral purple soil profiles, the P adsorption capability was mainly influenced by Fe-oxides and soil texture. Ca-bound P and Fe-Al-bound P represented the majority of the total inorganic P of calcareous soils. There was a saturation of adsorption capacity by sesquioxide and a high risk of dissoluble reactive P (NH4Cl-P) being released out of the soil profile in acidic and neutral purple soils after the greatest P addition, indicated by the higher proportions of NH4Cl-P (over 40%) and decreasing Fe-Al-P fraction. P fractions migrated with greater difficulty in calcareous purple soil profiles as Ca-P fraction peaked over 65% when adding a P dose at or greater than 80 g P kg-1, indicating the high potential of P adsorption. The X-Ray Diffraction analysis also verified the formation of brushite. Adaptive management practices should be designed to alleviate P losses for acidic and neutral purple soils.

Past studies have shown that dissolved organic carbon (DOC) washing can effectively remove heavy metals from contaminated soil. In this study, we used alkaline DOC solutions for remediation of arse...

Soil aggregates consist of sand, silt, and clay size particles. Many of the clay size particles in soils are clay minerals, which actively influence soil behavior. The properties of clay minerals may change significantly as soil particle size decreases to the nanoscale; however, little information is available about these properties for the Ultisols in China. In the present study, the clay mineral components and structural characteristics of four particle-size fractions (i.e.

The objectives of this research were to study the effects of Na2SiO3 application on the uptake, translocation, and accumulation of Pb in rice and to investigate the mechanisms of Pb immobilization by Na2SiO3 in paddy rice soils and rice plants. Pot experiments were conducted using a Cd-Pb-Zn-polluted soil and Oryza sativa L. ssp. indica cv. Donglian 5. L3-edge X-ray absorption spectroscopy was used to identify Pb species in soils and roots. The results showed that the application of Na2SiO3 increased soil pH and available soil Si but decreased DTPA-extractable Pb in the soil. High dose of Na2SiO3 (12.5 g/kg) reduced the Pb level in brown rice as it inhibited Pb transfer from soil to rice grains, especially Pb transfer from the root to the stem. The Pb X-ray absorption near-edge spectroscopic analysis revealed that application of high dose of Na2SiO3 increased Pb-ferrihydrite and PbSiO3 precipitates in the soil and in the root while it reduced Pb-humic acids (Pb-HAs) in the soil and Pb-pectin in the root. The decrease in Pb availability in the soil can be partly attributed to increase the precipitation of PbSiO3 and the association of Pb2+ with Fe oxides in the soil. The inhibition of the root-to-stem translocation of Pb was partially due to the precipitation of PbSiO3 on the root surfaces or inside the roots.

In pursuit of highyield, blind application of a large number of nitrogen fertilizer in tea plantation has not only seriously affected the quality of tea, but also resulted in environmental degradat...

Phosphorus recovery in the form of struvite has been aroused in recent decades for its dual advantages in eutrophication control and resource protection. The usage of the struvite products is normally determined by the size which is largely depended on the hydrodynamics. In this study, flow behavior of struvite pellets was simulated by means of Eulerian-Eulerian two-fluid model combining with kinetic theory of granular flow in a liquid-solid fluidized bed reactor (FBR). A parametric study including the mesh size, time step, discretization strategy, turbulent model and drag model was first developed, followed by the evaluations of crucial operational conditions, particle characteristics and reactor shapes. The results showed that a cold model with the mesh resolution of 16×240, default time step of 0.001sec and first order discretization scheme was accurate enough to describe the fluidization. The struvite holdup profile using Syamlal-O'Brien drag model was best fitted to the experimental data as compared with other drag models and the empirical Richardson-Zaki equation. Regarding the model evaluation, it showed that liquid velocity and particle size played important roles on both solid holdups and velocities. The reactor diameter only influenced the solid velocity while the static bed height almost took no effect. These results are direct and can be applied to guide the operation and process control of the struvite fluidization. Moreover, the model parameters can also be used as the basic settings in further crystallization simulations.

Increasing temperature and nitrogen (N) deposition are major drivers of global change that will influence plant-soil systems. We aimed to understand how plant stoichiometry and nutrient limiting types could change with continued warming and N inputs in subtropical regions. In 2014, the experiments were established in 30 mini-plots (2 × 2 m) with the following treatments: control, high N addition, low N addition, warming, warming + high N addition, and warming + low N addition. We sampled the leaf and root of Cunninghamia lanceolata and soils to assess their elemental and stoichiometric variables and δ15N under all six conditions. Both experimental warming and N fertilization consistently induced an increase in fine-root N, P, and N:P. The N:P ratio of the mature green-leaf and soil was 7.24–11.63 and 4.79–6.56, respectively. On average, C. lanceolata showed higher proportional P resorption, but lower N resorption. The δ15N enrichment factor significantly increased in the warming and N addition treatments. N addition decrease leaf N content, and increased the plant growth, which was due to the effect of the N dilution of C. lanceolata. In subtropical regions, N-limitation affects the growth of C. lanceolata, and the concurrent increase in warming and N fertilization should help relieve N-limiting conditions.

The suitability of an agent for washing heavy metal contaminated soils depends not only on the efficiency of heavy metal removal but also on the persistence of the washing effect, especially for agricultural soil. Redistribution of residual heavy metals in washed soil from inert pools to labile pools can reverse the initial washing effect. In order to study the redistribution of residual Pb in Pb-contaminated soils washed with citric acid (CA), ethylenediaminetetraacetic acid (EDTA), FeCl3, and HCl solutions, washed soils were incubated under both flood and 70% field water capacity (FWC) conditions for 180 days. The Pb availability in CA-, EDTA-, FeCl3-, and HCl-washed soils varied with incubation time. Diethylenetriaminepentaacetic acid (DTPA)-Pb generally increased with incubation time, except in CA-washed soil under flood incubation condition. Pb associated with the exchangeable/acid extractable fraction (F1) increased, whereas Pb in the easily reducible fraction (F2) decreased over time, for all washed soils under flood incubation condition; the changes in the amount of Pb associated with each fraction were much smaller under 70% FWC incubation. The transformation of Pb from F2 to F1 during flood incubation was largely caused by the mobilization of Fe and Mn oxides. The mobility factors (MF) of Pb for samples under flood incubation increased with increasing incubation time while those for samples under 70% FWC incubation changed only slightly, which implies increasing environmental risks of Pb from washed soils that are flooded. Therefore, the redistribution and potential environmental risks posed by heavy metals in washed soils, especially in paddy rice soils, should be taken into account when the suitability of a washing agent is evaluated. In the present study, CA was found to be unsuitable for washing Pb-contaminated agricultural soil, whereas the FeCl3 solution was the most stable washing agent tested, as it had high removal efficiency and low release of Pb after washing.

Mainly located in the Sichuan Basin, known as the ‘Land of Plenty’, purple soils (developed from purple sandstone and shale) have been long noted as highly productive in spite of their rocky texture. However, information on the physicochemical properties (including mineral properties) of purple soils remained obscure for the scientific community. For example, it is not clear what causes the purple color of the soils. In this study, eight soil profiles of the Jiufeng (JF, acidic), Shibao (SB, neutral), and Yanting (YT, calcareous) areas, representing the three most widely distributed purple soils in Sichuan Basin, were individually sampled under both cropland and forestland, and then analyzed using common chemical analysis and conventional X-ray diffraction to clarify the effects of clay mineral and anthropogenic influences on the typical soils. The results show that considerable variability of soil pH and cation-exchange capacity (CEC) exists between soil types (p

Fluidized bed reactor (FBR) has been applied in phosphorus recovery from wastewater due to its ability on producing struvite pellets with large size, high crushing strength and purity. However, the fine struvite crystals (fines) can be flushed out of the reactor, which may result in undesirable and variable phosphorus recovery efficiencies. In this study, the influences of key factors with respect to phosphorus recovery and product quality in a FBR were investigated for the treatment of swine wastewater. The effects of process parameters were first evaluated using response surface methodology (RSM), and later, long-term pilot-scale operations were tested. Results showed that fines retention was directly related to the in-reactor saturation index (SI) and upflow velocity (vup). Decreasing SI (from 2.42 to 1.65) or vup (from 75 to 25 mm s− 1) will reduce the fines entrainment and improve the phosphorus recovery profile by 14.9 and 18.5%, respectively. Moreover, these two factors governed the quality of the struvite pellets in the pilot-scale investigations—SI showed more crucial effect to size distribution, crushing strength and morphology than vup. As to the composition, struvite (35.5–95.3% of mass fraction) and CaCO3 (2.8 to 51.4% of mass fraction) were the two major components in the pellets. Decreasing SI or increasing vup and pellet size can enhance the struvite purity. Therefore, phosphorus recovery and pellet quality can be simultaneously improved by SI and vup control without additional trapping devices or reagents. The finding is constructive for FBR system set-up and operation in either pilot- or full-scale applications, where different phosphorus recovery rates and product qualities are required.

Hydrotalcite (HT) is a layered double hydroxide (LDH), which is considered as a potential adsorbent to remove anion contaminants. In this study, adsorption of chromate (CrO4) and phosphate (PO4) on HT was conducted at various pH and temperatures. Related adsorption mechanisms were determined via the isotherm, kinetic, and competitive adsorption studies as well as the Cr K-edge X-ray absorption fine-structure (XAFS) spectroscopy. The maximum adsorption capacities for CrO4 and PO4 on HT were 0.16 and 0.23 mmol g−1. Regarding adsorption kinetics, CrO4 and PO4 adsorption on HT could be well described by the second order model, and the rate coefficient of CrO4 and PO4 on HT decreased significantly with the increasing pH from 5 to 9. The adsorption kinetics for CrO4 and PO4 were divided into fast and slow stages with the boundary at 15 min. This biphasic adsorption behavior might be partially attributed to multiple reactive pathways including anion exchange and surface complexation. Fitting results of Cr K-edge EXAFS analysis showed a direct bonding between CrO4 and Al on HT surfaces. Such a surface complexation appeared to be the rate-limiting step for CrO4 adsorption on HT. By contrast, the diffusion through the hydrated interlayer space of HT was the major rate-limiting step for PO4. This study determined the adsorption behaviors of CrO4 and PO4 on HT, including the initial transfer process and the subsequent adsorption mechanisms. Such information could improve the strategy to use HT as the potential adsorbent for the remediation of anionic pollutants.

The presence and formation of hydroxy-interlayered minerals in the Holocene paleosol at the Wugong profile on the southernmost Chinese Loess Plateau were investigated by examining the < 1 μm and 1–2 μm clay fractions of the 50–150 cm horizon by Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). Prior to the analyses free Al and Fe phases were removed by dithionite-citric-bicarbonate (DCB) extraction. XRD patterns were obtained with air-dried, Mg-saturated, Mg-saturated with glycerol solvation (Mg-glycerol) and K-saturated and heated at 110, 250, 350, 450 and 550 °C samples both before and after hydroxy-interlayered materials removal by sodium citrate extraction. The absorption bands at 3699 and 3430 cm− 1 in the FTIR spectra of both sub-fractions indicated the presence of hydroxy-interlayered minerals. The K-saturated and heated XRD patterns confirmed this by the progressive collapse of the 1.4 nm reflection to a 1.0 nm reflection. After removal of the hydroxy-interlayered materials no obvious increase of the relative XRD intensity of the 1.8 nm reflection in Mg-glycerol pattern was observed and the 1.4 nm reflection exhibited a stronger collapse to 1.0 nm after K-saturation and increasing temperature treatment. This indicated that the hydroxy-interlayered minerals in the Holocene paleosol were mainly composed of hydroxyl-interlayer vermiculite. The hydroxyl-interlayer vermiculite was formed by the polymerization of Al/Fe-hydroxy materials within the interlayer space of vermiculite. Shoulder-like reflection at 1.2 nm in the K-550 °C pattern of the 1–2 μm fraction indicated a higher degree of Al/Fe-hydroxylation in the coarse fraction than in the fine fraction, which was consistent with the lower extractable Al and Fe in the coarse fraction. The reflection at 1.38 nm in the K-550 °C pattern could be interpreted as pedogenic chlorite. Thus, transformation of vermiculite into hydroxy-interlayered vermiculite and finally into a chlorite-like mineral (pedogenic chlorite) has occurred in the Holocene paleosol on the southernmost Chinese Loess Plateau.

A Gram-stain-positive, rod-shaped, endospore-forming, aerobic bacterium (FJAT-14571T) was isolated from a soil sample in Taiwan. Strain FJAT-14571T grew at 20–40 °C (optimum 35 °C), pH 6–10 (optimum pH 8) and 0–2 % (w/v) NaCl (optimum 0 %). Phylogenetic analyses based on 16S rRNA gene sequences showed that strain FJAT-14571T was a member of the genus Bacillus and was most closely related to Bacillus oceanisediminis DSM 24771T (96.2 %). DNA–DNA relatedness between strain FJAT-14571T and B. oceanisediminis DSM 24771T was low (32.0 % ± 0.88 %). The diagnostic diamino acid of the peptidoglycan of strain FJAT-14571T was meso-diaminopimelic acid and the predominant menaquinone was MK-7 (96.6 %). The major cellular fatty acids were iso-C15 : 0 (46.4 %), anteiso-C15 : 0 (7.6 %), iso-C17 : 0 (8.2 %) and iso-C16 : 0 (10.0 %) and the DNA G+C content was 40.8 mol%. Phenotypic, chemotaxonomic and genotypic properties clearly indicated that strain FJAT-14571T represents a novel species within the genus Bacillus, for which the name Bacillus taiwanensis sp. nov. is proposed. The type strain is FJAT-14571T ( = DSM 27845T = CGMCC1.1 2698T).

The effectiveness of four different washing extractants--HCl, FeCl3, citric acid, and EDTA--in removing Cd, Pb, and Zn from polluted soil was studied. The removal of these metals, their redistribution between fractions, and the potential risks posed by them, in soils washed with the tested extractants, were examined. Although all the rounds of washing removed Cd, Pb, and Zn from soil, the first round removed more metals than subsequent rounds. Each of the four extractants had different effects on the removal of the metals. At the end of the first round of washing, HCl, EDTA, and FeCl3 were the most effective in removing Zn, Pb, and Cd, respectively. Both the single round and five successive rounds of washing with various extractants resulted in significant increases in Pb in the exchangeable/acid extractable fraction. Washing with HCl, EDTA, and FeCl3 significantly reduced potential risks (calculated as the Potential Risk Index, PRI) posed by Cd in washed soil. The first round of washing, using all extractants, increased the risks posed by Pb and Zn. However, five successive rounds of washing with FeCl3 and EDTA reduced the risk posed by Pb, and washing with citric acid and FeCl3 increased the risks posed by Zn. EDTA and HCl were better for reducing Zn risks, and successive washing with EDTA and FeCl3 were more effective in reducing Pb risks than the other extractants. Finally, five successive rounds of washing, with all the extractants, effectively reduced the potential risks posed by Cd. Among the four reagents, EDTA was advised to be the alternative of the washing reagent by significantly reducing the PRI values of Cd, Pb, and Zn.

Removal of arsenic (As) from water supplies is needed to reduce As exposure through drinking water and food consumption in many regions of the world. Magnetite nanoparticles (MNPs) are promising and novel adsorbents for As removal because of their great adsorption capacity for As and easy separation. This study aimed to investigate the adsorption mechanism of arsenate, As(V), and arsenite, As(III), on MNPs by macroscopic adsorption experiments in combination with thermodynamic calculation and microspectroscopic characterization using synchrotron-radiation-based X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). Adsorption reactions are favorable endothermic processes as evidenced by increased adsorption with increasing temperatures, and high positive enthalpy change. EXAFS spectra suggested predominant formation of bidentate binuclear corner-sharing complexes ((2)C) for As(V), and tridentate hexanuclear corner-sharing ((3)C) complexes for As(III) on MNP surfaces. The macroscopic and microscopic data conclusively identified the formation of inner-sphere complexes between As and MNP surfaces. More intriguingly, XANES and XPS results revealed complex redox transformation of the adsorbed As on MNPs exposed to air: Concomitant with the oxidation of MNPs, the oxidation of As(III) and MNPs was expected, but the observed As(V) reduction was surprising because of the role played by the reactive Fe(II).

The relationships between the basic properties and trace elements in soil argillans and corresponding matrix soils were studied by sampling from the B horizons of 26 Alfisols in croplands of the subtropical area in Central China. The soil elements (K, Na, Ca, Mg, Mn, Co, Cu, Cr, Cd, Li, Mo, Ni, Pb, Ti, V, and Zn) were extracted by acid digestion and their contents were measured using inductively coupled plasma optical emission spectrometry (ICP-OES). The mean contents of clay and organic matter in the argillans were approximately 1.1 and 1.3 times greater than those in the matrix soils, respectively. The pH values and the contents of P2O5 and bases (K2O, Na2O, CaO, and MgO) in the argillans were higher than those in the corresponding matrix soils. Cu, Cd, Ti, and V were enriched in the argillans. Correlation coefficients and factor analyses showed that Co, Cu, Li, and Zn were bound with phyllosilicates and manganese oxides (Mn-oxides) in the argillans. Cr and Pb were mainly associated with iron oxides (Fe-oxides), while Ni was bound with Mn-oxides. Cd, Ti, and V were chiefly associated with phyllosilicates, but Cr and Mo were rarely enriched in the argillans. In contrast, in the matrix soils, Co and Zn were associated with organic matter and Fe-oxides, Cr existed in phyllosilicates, and Mo was bound to Fe-oxides. Cd, Ti, and V were associated with organic matter. The results of this study suggest that clays, organic matter, and minerals in the argillans dominate the illuviation of trace elements in Alfisols. Argillans might be the active interfaces of elemental exchange and nutrient supply in cropland soils in Central China.

Soil clays (< 2,000 nm) (SC) and soil nanoclays (< 100 nm) (SNC) were used as adsorbents for removal of Cu(II) from aqueous solution. The experiments were conducted with variables including pH, interaction time, concentration of Cu(II) and temperature. Four kinetic models have been employed to investigate adsorption mechanisms, and the experimental data more closely resemble a second-order process of the kinetic model. Adsorption studies on soil nanoclays have been shown to be highly effective in removing of Cu(II) from aqueous solution. This adsorbent is widely available as a natural material, is mechanically stable and, most importantly, it is environmentally appealing. The maximum Cu(II) adsorption capacity of soil nanoclays (31.7 mg/g) is more than three times higher than natural soil clays (10.2 mg/g). Our study demonstrates that soil nanoclays can be used effectively for removal of Cu(II) from aqueous systems to achieve environmental cleaning purposes.

Wine-processing waste sludge and alkaline substances, including KOH, NaOH, Ca(OH) 2 , and Mg(OH) 2 , were employed to prepare various dissolved organic carbon (DOC) solutions for remediating a Pb-contaminated cropland by soil washing. The Pb concentrations were 5340 and 4920 mg kg − 1 in the topsoil and subsoil, respectively. Aqueous solution treatment , general DOC treatment , and enhanced DOC treatment were proposed as treatments for the reclamation and determination of the factors affecting the removal of Pb, such as pH, initial concentration of the DOC solution, temperature, and washing frequency. The aqueous solution treatment could not remove sufficient Pb and therefore failed in the reclamation. Approximately 86.5% Pb was removed from the topsoil at pH 2.0 by the general DOC treatment undergoing two wash cycles. However, over 90% Pb was removed from the subsoil under the same conditions; only the final Pb concentration in the subsoil met the control standard, 500 mg kg − 1 . About 93% Pb in the topsoil could be removed at pH 3.0 by the enhanced DOC treatment, which was performed using a 2500 mg L − 1 DOC solution containing abundant Ca 2 + and Mg 2 + at an 80:1 liquid/soil ratio (v/v) at 40 °C for 60 min. Meanwhile, organic matter, cation exchange capacity, NH 4 + -N, as well as exchangeable K, Ca, and Mg contents increased by 125%, 22.6%, 107%, 577%, 55.3%, and 306%, respectively, and the pH in the topsoil decreased to 3.7. The use of Ca(OH) 2 and Mg(OH) 2 not only prevented washing losses of the exchangeable Ca and Mg but also increased Pb removal by 20%. However, its use decreased the availability of P in the soil.

Background Clay minerals especially organoclays modified by the introduction of organic molecules into the mineral structure show much promise for environmental remediation applications. Application of organic attapulgite (O-APG) and organic montmorillonite (O-MMT) as soil amendments to bind polychlorinated biphenyl (PCB) in contaminated soils and observe PCBs accumulated in the ryegrass shoots and roots was investigated. Results Pot experiments in greenhouse indicated that organoclays could significantly fix the PCB in soils and reduce its contents in ryegrass shoots and roots. Compared with the control, the migration of concentrations of PCB into the environment in contaminated soils is reduced by about 28.5 and 44.1%, and concentrations of PCB in ryegrass roots and shoots were reduced within the range from 57.0 to 63.0% and 49.6 to 56.5%, respectively, through addition of 6% organic attapulgite and montmorillonite. There was a negative correlation between the accumulation of PCB in ryegrass and the amount of organoclay addition. The accumulations of PCB in ryegrass roots were significantly higher than those in the ryegrass shoots. Conclusions The two organoclays had been proved effective as environmental amendments for reducing the mobility and bioavailability of PCB in contaminated soils. The results of this study provided an efficient method for the remediation of PCB contaminated soils.

The release of silicon (Si) from and the structural changes to clay minerals (i.e., kaolinite, montmorillonite (Mt), and illite) were investigated after being batch incubated with low-molecular-mass organic acids (i.e., oxalic and citric acids, LMMOA) of varying concentrations (0–0.5 mol L − 1 ) at 25 °C. Two mineral acids (i.e., HCl and H 2 SO 4 ) with varying concentrations were also reacted with Ca-montmorillonite (Ca 2 + -Mt). With increasing reaction time, the Si released from kaolinite and illite reached its maximum level after incubation with the varying LMMOA concentrations for 15 days. Quantities of Si released from the clay minerals with the LMMOA ranged from 0.22 to 114.01 μg mL − 1 (Si). Quantity of Si released with oxalic acid was higher than that with citric acid. The Si released from the clay minerals increased with increasing organic acid concentrations. More Si was released from Mt than from kaolinite and illite when incubated with the same LMMOA concentration. With increasing organic acid concentrations, the X-ray diffraction (XRD) reflection intensities of the Mt weakened, and this trend was more remarkable in the clay treated with oxalic acid than citric acid. However, no relationship between the XRD reflection intensity and the acid concentrations was noticeable in the incubated kaolinite and illite. While incubating with hydrochloric acid (HCl) and sulfate acid (H 2 SO 4 ) for 15 day incubation, amounts of Si released from Ca 2 + -Mt were generally higher than those reacting with organic acids, and more Si was released in the H 2 SO 4 treatment than that of HCl. But the XRD reflection intensities of the Ca 2 + -Mt had no distinctly change compared with those treated with the organic acids.

This study investigates biogeochemical reductive release of arsenate from beudantite into solution in a crater area in northern Taiwan, using a combination of X-ray absorption near-edge structure (XANES) and atomic absorption spectrometry. Total arsenic (As) concentrations in the soil were more than 200 mg/kg. Over four months of laboratory experiments, less than 0.8% As was released into solution after reduction experiments. The 71% to 83% As was chemically reduced into arsenite (As(III)) and partially weathering into the soluble phase. The kinetic dissolution and re-precipitation of As, Fe, Pb and sulfate in this area of paddy soils merits further study.

The products of Al hydrolysis play significant roles in terrestrial and aquatic environments, particularly through their binding of nutrients and pollutants. However, the effect of catechins on the crystallization of Al precipitates and the resultant surface alteration of Al transformation products on their kinetics and mechanisms of adsorption of Cd still remain to be uncovered. The objective of this paper was to investigate the kinetics of Cd adsorption on the Al precipitates formed under the influence of catechin. The experiments were conducted with initial catechin/Al molar ratios, interaction time, concentration of Cd ions, and temperature as the variables. Six kinetic models were employed to investigate adsorption mechanisms, and data resembled more closely a second-order process. The structural perturbation of Al precipitates by catechin, resulting in the development of their microporosity and alteration of surface and charge properties, substantially enhanced the rate constants of both fast and sl...

This study aimed to determine effects of rice straw biochar on Pb sequestration in a soil-rice system. Pot experiments were conducted with rice plants in Pb-contaminated paddy soils that had been amended with 0, 2.5, and 5% (w/w) biochar. Compared to the control treatment, amendment with 5% biochar resulted in 54 and 94% decreases in the acid soluble and CaCl2-extractable Pb, respectively, in soils containing rice plants at the maturity stage. The amount of Fe-plaque on root surfaces and the Pb concentrations of the Fe-plaque were also reduced in biochar amended soils. Furthermore, lead species in rice roots were determined using Pb L3-edge X-ray absorption near edge structure (XANES), and although Pb-ferrihydrite complexes dominated Pb inventories, increasing amounts of organic complexes like Pb-pectins and Pb-cysteine were found in roots from the 5% biochar treatments. Such organic complexes might impede Pb translocation from root to shoot and subsequently reduce Pb accumulation in rice with biochar amendment.

Wine processing waste sludge (WPWS) has been shown to be an effective sorbent for sorption of nickel, lead, and chromium, but the sorption of copper (Cu) in aqueous solution by WPWS has not been conducted. The objective of this study was to explore the sorption mechanism of WPWS for copper. Infrared analysis revealed carboxyl was the major functional group inWPWS. The WPWS sorption isotherms of copper were only well described by Langmuir sorption isotherm. The maximum adsorption capacity (Qm) was 14.26 mg/g at 50 8C. A pseudo- second-order sorption kinetic model successfully described the kinetics of copper sorption onto WPWS. The Gibb free energies (DG8) ranged from � 20.69 to � 24.29 kJ mol -1 , and the DH8 and DS8 were 5.048 kJ mol -1 and 91.05 J mol -1 K -1 , respectively. The trend of the intra-particular diffusion rate is the opposite of the adsorption constant of the pseudo- second-order equation. Water Environ. Res., 84, 733 (2012).

This study examined the change in the speciation of cadmium (Cd) in contaminated rice paddy soils with prolonged submergence. Three Changhua soils (CH1, CH2, and CH3) from central Taiwan and three Taoyuan red soils (TY1, TY2, and TY3) from northern Taiwan with different levels of heavy metal contamination were selected for the study. The Cd, Fe, Mn, soil pH, and Eh in soil solutions were determined as a function of submerging time. During submergence, the Fe and Mn concentration increased, while the SO4 2− concentration decreased. The concentrations of Cd immediately increased in the soil solutions after a short submerging time and then decreased with further submergence. The sequential extraction showed that the exchangeable fraction decreased and the oxide-bound fraction increased after submergence. According to preliminary calculations of the MinteqA2 program, sulfate cannot be reduced to sulfite or sulfide under the soil Eh and pH values observed for the soils after prolonged submergence. Thus, the observed decreases of sulfate concentration may result from sulfate reduction in the micro-environments, which cannot be accounted for by the thermodynamic calculation. The reduction of sulfate to sulfide may subsequently result in the formation of CdS precipitate, which attributes to the decreases of Cd concentrations in the soil solutions after prolonged submergence.

Sewage sludge (SS) is used on sloping land, as a soil amendment, because of its organic matter (OM) and nutrient content. However, the presence of nitrogen (N), in acidic soils amended with sludge, and its transport in runoff can lead to eutrophication of downstream surface water. This study assesses the effects of different application methods on N transport, via runoff from plots amended with SS (0 and 120 Mg ha−1). A lateritic red soil (pH 5.2) was selected for this study, using simulated rainfall conditions. When sludge was broadcasted and mixed with surface soils (BM), the concentrations and mass losses of total N in the mixed sample (MTN), total N in the settled sample (STN), total particulate N (TPN), total suspended N (TSN), total dissolved N (TDN) and NH4+-N, in runoff water, were highest at 1 or 18 d after application. BM treatments showed initial pollution risks to surface waters, which diminished gradually with time. Whereas the concentrations and mass losses of NO3−-N, in all sludge plots, appeared to have a declining trend, after an initial ascent. Hole-application (HA) and broadcast application with hay mulch (BH) treatments prevented N loss effectively, the runoff losses coefficient of MTN increased in the order BM (0.43%) > HA (0.15%) > BH (0.03%). For sludge treatments, N was largely lost in dissolved species, while a large portion of NH4+-N was lost in particulate fraction. Nitrogen (N) losses in runoff were greatly affected by the transformation of sludge N in the soil and the modification of soil properties, induced by sludge amendment. The risk associated with the application of sludge to sloping fields, in areas of acidic soil, is an important research subject that merits further study.

Using intumescent coatings on wood-based materials is an effective method for fire safety. Previous studies have demonstrated that the formulation of components strongly influences the performance of coatings. This study investigated the effect of intumescent formulation of vinyl acetate-acrylic coating on flame retardancy of plywood. The fire retardancy of materials was assessed by both heat release and CO and CO2 emissions. The CO and CO2 emissions have not been used frequently to rank materials; the highly toxic CO and CO2 may cause most fire fatalities. The fire retardancy of coatings on plywood was assessed by a cone calorimeter. Total heat release and time to peak heat release rate were the two primary parameters. The data show that low contents of binder resin (BR) and foam producing substance (FPS) decreased total heat release and lengthened time to peak heat release rate. Additionally, low BR and FPS content can form an ideal char layer. The ideal char layer significantly decreased the CO and CO2 emission. The mechanism to achieve better fire performance was verified by thermogravimetrical analysis exhibiting lower weight loss. Moreover, evaluated by 31P NMR, the low BR and FPS content can extend the survival duration of phosphor-carbonaceous chars. The results provide information for designing vinyl acetate-acrylic emulsion coating.

Information on the physicochemical properties, mineral species and micromorphology of lateritic soils and gravel soil layers in paleo-environmental soil profile is severely lacking. Red soil profile of the Taoyuan terrace was employed to demonstrate its different extents of lateritic weathering. The objectives of this study were to compare the physicochemical properties of lateritic soils and gravel soil layers and identify using conventional and synchrotron X-ray diffraction (XRD) analyses mineral species in nanoparticles separated by automated ultrafiltration device (AUD) apparatus. Soil samples were collected from paleo-environmental lateritic soils. Soil samples were examined using elemental analysis, conventional and synchrotron XRD analyses, high gradient magnetic separation, separation and collection of nanoparticles by AUD apparatus, and transmission electron microscopy (TEM). The soil pH, redness index, quantities of free Al- and Fe-oxides (Ald and Fed), and clay content of lateritic soils are higher than those of gravel soil layers. Illite, kaolinite, gibbsite, quartz, goethite, and hematite were identified in clay fractions and nanoparticles by conventional and synchrotron XRD analyses. TEM images show presence of hematite nanoparticles on the surface coating of kaolinite nanoparticles and aggregated hematite nanoparticles overlapping the edge of a kaolinite flake in a size range of 4–7 nm. Synchrotron XRD techniques are more straightforward and powerful than conventional XRD with random powder methods for identifying nanoparticles in red soils, particularly for illite, kaolinite, goethite, and hematite nanoparticles. According to chemical compositions of clay fractions and red soil features in the Taoyuan terrace, these red soils can be taken as lateritic red earths or red earths. This work suggests that physicochemical properties, mineral species, and micromorphology of red soil at all depths can shed light on the extent of paleo-environmental lateritic weathering.

Dye wastewaters usually contain toxins and high chroma, making them difficult to treat with biological methods. The adsorption process plays an important role in removing dyes from wastewaters. This study aimed to explore the methylene blue (MB) adsorption mechanism by wine-processing waste sludge (WPWS). The WPWS contains a high cation-exchange capacity (64.2 cmol c kg −1 ) and organic matter (52.8%). The parameters affecting MB adsorption included pH, initial concentration of MB, reaction temperature, particle size and dosage of WPWS. The WPWS adsorption isotherms of MB were only well described by Langmuir adsorption isotherm. The maximum adsorption capacity ( Q m ) of MB was 285.7 mg g −1 at 25 °C. The activation energy determined by Arrhenius equation is 29.995 kJ mol −1 . Under steady-state reaction conditions, the Gibb free energy (Δ G °) ranged from −24.607 to −27.092 kJ mol −1 and Δ H ° was −8.926 kJ mol −1 , indicating that lower reaction temperature would favor MB adsorption. Therefore, MB adsorption by WPWS was a spontaneous, exothermic and physisorption reaction.

Humic substances are a major component of soil organic matter that influence the behavior and fate of heavy metals such as Cr(VI), a toxic and carcinogenic element. In the study, a repetitive extraction technique was used to fractionate humic acids (HAs) from a peat soil into three fractions (denoted as F1, F2, and F3), and the relative importance of O-containing aromatic and aliphatic domains in humic substances for scavenging Cr(VI) was addressed at pH 1. Spectroscopic analyses indicated that the concentrations of aromatic C and O-containing functional groups decreased with a progressive extraction as follows: F1 > F2 > F3. Cr(VI) removal by HA proceeded slowly, but it was enhanced when light was applied due to the production of efficient reductants, such as superoxide radical and H2O2, for Cr(VI). Higher aromatic- and O-containing F1 fraction exhibited a greater efficiency for Cr(VI) reduction (with a removal rate of ca. 2.89 mmol g−1 HA under illumination for 3 h). 13C NMR and FTIR spectra further demonstrated that the carboxyl groups were primarily responsible for Cr(VI) reduction. This study implied the mobility and fate of Cr(VI) would be greatly inhibited in the environments containing such organic groups.

Purpose Biochar amendments can alter phosphorus (P) availability in soils, though the influencing mechanisms are not yet fully understood. This work investigated the adsorption and desorption of P on ferrihydrite (F, a Fe-oxide widely distributed in surface environments) in order to evaluate the interactions between P and Fe-oxide in the absence or presence of biochar (F or ferrihydrite–biochar (F–B) interaction) in soils.

BACKGROUND: Tea plants are always cultivated in acid soils in hilly regions and their growth can be dependent on to soluble aluminium (Al). The mechanism of Al detoxification and the influence of Al on phenolic compounds (i.e. catechin) in the roots of tea plants has remained obscure. This study aimed to investigate the influence of Al changes on the concentrations of phenolic substances in tea plants through hydroponic experiments. RESULTS: Tea plants were cultivated in nutrient solution containing 1.5 and 2.5 mmol L−1 Al, and these treatments enhanced the growth of new buds and roots. Aluminium stimulated the uptake of Ca, Mg, K and Mn, whereas the uptake of Fe, Cu and Zn was retarded. Moreover, total phenol concentrations in tea plant tissues increased with increasing Al concentrations. In general, catechin concentrations in leaves increased with increasing Al concentrations in the hydroponic experiments. High correlation coefficients were obtained between Al and (−)-ECG (r2 = 0.85, P < 0.01) and between Al and total phenols (r2 = 0.92, P < 0.01). CONCLUSIONS: The Al concentration in tea plants indeed increases catechin concentrations and plays an important role in the growth of tea plants. Copyright © 2011 Society of Chemical Industry

Attapulgite and montmorillonite were utilized to remediate heavy metal polluted red soils in Guixi City, Jiangxi Province, China. The effects of clay minerals on availability, chemical distribution, and biotoxicity of Cu and Zn were evaluated. The results provided a reference for the rational application of clay materials to remediate heavy metal contaminated soils. From the sorption experiment, the maximum adsorbed Cu2+ by attapulgite and montmorillonite was 1501 and 3741 mg/kg, respectively. After polluted red soil was amended with attapulgite or montmorillonite and cultured at 30 and 60 days, soil pH increased significantly compared to the control. An 8% increase in the amount of montmorillonite in soil and 30 days incubation decreased acid exchangeable Cu by 24.7% compared to the control red soil. Acid exchangeable Cu decreased with increasing amounts of attapulgite and montmorillonite, with best remediation effect reached at a dose of 8%. Results also showed that the Cu poisoning effect on earthworms was reduced with the addition of attapulgite and montmorillonite. Montmorillonite showed the best effect, with the addition of a 2% dose the mortality of earthworms decreased from 60% to zero compared to the control. Our results indicated that the bioavailability of Cu in soils was reduced more effectively with the application of montmorillonite than attapulgite.

Wine processing waste sludge (WPWS) has shown effective removal of heavy metals in batch studies, but the adsorption in a fixed-bed WPWS column has not been examined and the mass transport in this column remains unclear. This study aimed to investigate: (1) the retardation factor ( R ) and the dispersion coefficient ( D ) of WPWS, employing one-dimensional convective–dispersive model with breakthrough curve (BTC) and using chromium, copper and zinc as the adsorbates; and (2) explore the adsorption mechanism of WPWS column for heavy metals. The retardation factor for various metal treatments is shown in the following order: Cr(18.3) > Cu(13.0) > Zn(7.2), indicating their binding affinity toward WPWS. The dispersion coefficients were calculated to be 2.36 × 10 −6 , 5.89 × 10 −7 and 6.83 × 10 −7 m 2 s −1 for Cr, Cu and Zn treatments, respectively. The high charge density for Cr 3+ ion makes it longer for the Cr column to attain exhaustion state, about 4.0 and 8.2 times the time required for the Cr and Zn columns. However, the least retardation and adsorption amount for Zn can be attributed to its full orbital in electronic configuration.

Cadmium (Cd)-contaminated soils are of concern because of their possible effects on ecosystems and human health. Millet (Setaria italica (L.) Beauv.) is moderately tolerant to salinity and poor soil fertility as well as pristine soils contaminated with trace elements. It has been hypothesized that low-molecular-weight organic acids (LMWOA) exuded into the rhizosphere may play important roles in Cd uptake by millet. Thus the objectives of this study were to assess the LMWOA exudations of millet in Cd-contaminated soils and to evaluate the capacity of millet to remove Cd for phytoremediation. Millet was grown for 3 weeks in soils containing between 0 and 1,000 mg Cd kg−1. These soils and plant tissues were analyzed for Cd content after harvest. The Cd accumulated in millet tissues was significantly increased with increasing Cd-amended rate. The total LMWOA concentrations in root exudates were significantly correlated with the amount of Cd accumulated in millet shoots and roots. High levels of Cd amendment stimulated secretion of LMWOA, a process capable of reducing Cd toxicity via the formation of Cd-organic complexes (Cd-LMWOA), thereby detoxifying the contaminated soil.

Contents and properties of heavy elements in iron-manganese cutans and the corresponding matrix soils of three subtropical Chinese soils (Fragiudalf, Ferrudalf, and Hapludult) were investigated to discern the effect of soil-forming factors on the enrichment of heavy elements in the iron-manganese cutans with respect to the matrices. Results showed that the contents of clay, organic matter (OM), bases, and heavy metal elements were higher in the cutans than in the matrices. Cutans in the Fragiudalf had a neutral pH and higher content of OM and bases than those in the other soils. The cutans in the Ferrudalf were acidic, with increased contents of Fe and Mn oxides. The cutans in the Hapludult were more acidic and clayey than the cutans in the Fragiudalf and the Ferrudalf. Moreover, the contents of free Fe oxides and ratios of extractable noncrystalline Fe oxide/free Fe oxide (Feo/Fed) in the cutans of the Hapludult were higher than those in the other cutans. Compared with the corresponding matrices, the contents of heavy-metal elements in cutans of Hapludult increased more than those in other iron-manganese cutans. The varimax orthogonal factor rotation of factor analysis was chosen to make the statistical test a good fit to show the elemental distribution between the cutans and their corresponding matrices. The results revealed that Mn oxides played a leading role in the enrichment of most heavy metals for the cutans in the Fragiudalf. In the Ferrudalf, Fe oxides strengthen the migration process of the metals to the cutans. For the cutans in the Hapludult, the influence of Mn oxides on the enrichment of heavy metals decreased, and the impact of clay and Fe oxides increased with respect to the cutans in other soils. The factors that affected the heavy metals were the least for the cutans of the Ferrudalf compared with those in the cutans of the Fragiudalf and the Hapludult. The transport of heavy metals from the matrix soils to iron-manganese cutans in the three soils was mainly influenced by the different soil-forming environments and soil compositions. Statistical analysis indicated that the soil-forming factors that affected the enrichment of heavy metals in the cutans were more prominent in the Ferrudalf than in the Fragiudalf and the Hapludult.

Chemical surfactants or bio-surfactants intercalated into layered double hydroxides (LDHs) are considered as potential organic pollutant sorbents. This study evaluates the effects of (1) using either calcined or uncalcined LDH, and various solid/solution ratios, (2) the concentrations of the chemical surfactant sodium dodecyl sulfate (SDS) or the bio-surfactant rhamnolipid (RL), and (3) reaction temperatures and times on the synthesis of SDS-LDH and RL-LDH. Small angle X-ray diffraction (SAXRD) and X-ray diffraction (XRD) patterns reveal that using 1000 mg L−1 RL intercalated 2:1 uncalcined LDH with 3 days reaction time, 0.5 g L−1 solid/solution ratio, and temperature of 65 °C to synthesize the RL-LDH, containing more organic carbon content, showing larger interlayer distance than SDS-LDH. RL-LDH shows subsequent higher efficiency of naphthalene sorption than SDS-LDH, depending on higher organic carbon contents and larger interlayer distance of RL-LDH. Since RL-LDH is environmentally friendly chemical, these results are of practical interesting in RL-LDH could be potentially employed as a sorbent for removal organic contaminants from aqueous solutions, and particularly in optimizing aquatic environment remediation technologies.

Interactions of toxic Cr(VI) with renewable biomaterials are considered an important pathway for Cr(VI) removal in ecosystems. Biomaterials are susceptible to dissolution, and their dissolved derivatives may provide an alternative to surface-involved pathway for scavenging of Cr(VI). In this study, dissolved organic carbon (DOC) derived from Neurospora crassa biomass was investigated. The proportion of Cr(VI) reduction by DOC to that on biomass was determined to evaluate the importance of DOC to Cr(VI) reduction. A rapid increase in DOC concentration from 145.6 to 193.7 mg L(-1) was observed when N. crassa-biomass was immersed in 0.01 M KCl solution at pH of 1-5, and polysaccharides, peptides, and glycoproteins with carboxyl, amide, and -NH functional groups, are the major compositions of DOC. On reaction of 96.2 microM Cr(VI) with N. crassa-biomass or DOC, it was estimated that DOC contributed approximately 53.8-59.5% of the total Cr(VI) reduction on biomass in the dark. Illumination enhanced Cr(VI) reduction via photo-oxidation of biomass/DOC under aeration conditions, which formed superoxide for Cr(VI) reduction. At pH 1, photoinduced Cr(VI) reduction by DOC proceeded more rapidly than reduction on the biomass surface. However, at pH >3, with a decrease in Cr(VI) reduction by DOC, photon-excited biomass may become an important electron source for Cr(VI) photoreduction.

Todorokite-type manganese oxide octahedral molecular sieves (OMS-1) have been extensively studied due to their potential applications as materials. In this study, a nanofibrous todorokite-type, tun...

Todorokite is one common manganese oxide in soils and sediments and is commonly formed from layered Na-buserite. Aging processes can alter the physicochemical properties of freshly formed Na-buserite in natural environments. However, it is not clear whether and how aging affects the formation of todorokites. In the present paper, Na-buserite with aging treatment was employed to prepare todorokite at atmospheric pressure to investigate the effects of aging treatment of Na-buserite on the formation of todorokite. Four aged Na-buserite samples, which are produced through oxidation of Mn2+ in concentrated NaOH medium by O2 with aging for 3, 6, 9, and 12 months, were employed to investigate the effects of aging processes on the transformation from Na-buserite to todorokite by Mg2+-templating reaction at atmospheric pressure. The manganese oxides were examined using X-ray diffraction (XRD), elemental analysis, determinations of the average manganese oxidation number, infrared spectroscopy (IR), and transmission electron microscopy (TEM). The XRD, IR, and elemental analyses indicate that aging treatment can alter the substructure of the freshly synthesized Na-buserite. During the aging process, some of the Mn(III) may migrate into the interlayer region or disproportionate to form Mn2+ and Mn4+ from the layer of Na-buserite and the concomitant formation of layer vacancies. The interlayer Mn3+ or Mn2+ occupied above or below the layer vacancy sites and become corner-sharing octahedral. XRD analyses and TEM clearly show that the transformation from Na-buserite to todorokite was promoted by aging treatments. The alterations of substructure of aged Na-buserites can promote the rearrangement of manganese to construct a tunnel structure during the transformation from layered manganese oxides to tunnel-structure todorokite at atmospheric pressure. The transformation from Na-buserite to todorokite was promoted by aging treatments at atmospheric pressure, and it is more suitable to explore the origination of natural todorokite in Earth surface environments using aged layered manganese oxides.

The dynamics of Cs and Sr sorption by soils, especially in the subtropics and tropics, as influenced by soil components are not fully understood. The rates and capacities of Cs and Sr sorption by selected subtropical and tropical soils in Taiwan were investigated to facilitate our understanding of the transformation and dynamics of Cs and Sr in soils developed under highly weathering intensity. The Langmuir isotherms and kinetic rates of Cs and Sr sorption on the Ap1 and Bt1 horizons of the Long-Tan (Lt) and the A and Bt1 horizons of the Kuan-Shan (Kt), Mao-Lin (Tml) and Chi-Lo (Cl) soils were selected for this study. Air-dried soil (2mm) samples were reacted with of 7.5 x 10(-5) to 1.88 x 10(-3)M of CsCl (pH 4.0) or 1.14 x 10(-4) to 2.85 x 10(-3)M of SrCl(2) (pH 4.0) solutions at 25 degrees C. The sorption maximum capacity (q(m)) of Cs by the Ap1 and Bt1 horizons of the Lt soil (62.24 and 70.70 mmol Cs kg(-1) soil) were significantly (p0.05) higher than those by the A and Bt1 horizons of the Kt and Cl soils (26.46 and 27.49 mmol Cs kg(-1) soil in Kt soil and 34.83 and 29.96 mmol Cs kg(-1) soil in Cl soil, respectively), however, the sorption maximum capacity values of the Lt and Tml soils did not show significant differences. The amounts of pyrophosphate extractable Fe (Fe(p)) were correlated significantly with the Cs and Sr sorption capacities (for Cs sorption, r(2)=0.97, p1.0 x 10(-4); for Sr sorption, r(2)=0.82, p2.0 x 10(-3)). The partition coefficient of radiocesium sorbed on soil showed the following order: Cl soilKt soilTml soilLt soil. It was due to clay minerals. The second-order kinetic model was applied to the Cs and Sr sorption data. The rate constant of Cs or Sr sorption on the four soils was substantiality increased with increasing temperature. This is attributable to the availability of more energy for bond breaking and bond formation brought about by the higher temperatures. The rate constant of Cs sorption at 308 K was 1.39-2.09 times higher than that at 278K in the four soils. The activation energy of Cs and Sr sorbed by the four soils ranged from 7.2 to 16.7 kJ mol(-1) and from 15.2 to 22.4 kJ mol(-1), respectively. Therefore, the limiting step of the Cs(+) or Sr(2+) sorption on the soils was diffusion-controlled processes. The reactive components, which are significantly correlated with the Langmuir sorption maxima of Cs and Sr by these soils, substantially influenced their kinetic rates of Cs and Sr sorption. The data indicate that among components of the subtropical and tropical soils studied, short-range ordered sesquioxides especially Al- and Fe-oxides complexed with organics play important roles in influencing their capacity and dynamics of Cs and Sr sorption.

The relationship between organic matter contents and soil aggregates of particle size ranging from >4, 2–4, 1–2, 0.5–1 to 0.25–0.5 mm in three eroded (slightly, moderately and severely) Ultisols in central China was investigated using dry-sieving and wet-sieving methods, as well as chemical analyses. In different eroded Ultisols, the size distribution percentages of >4 and 2–4 mm macroaggregates obtained by dry-sieving method were all higher than that by wet-sieving method by separately between 12.3 and 45.7%, 3.0 and 24.7% , but the percentages of 0.25–0.5, 0.5–1 and 1–2 mm macroaggregates showed opposite trend. Microaggregates ( 0.25 mm water-stable aggregates (WSA) and average of mean weight diameter (MWD) decreased from slightly eroded soil to severely eroded soil by 28.0% and 0.14 mm, respectively. The organic matter (OM) content of macroaggregate fractions from slightly and moderately eroded Ultisols rose with increasing in particle size fractions from 0.25–0.5 to >4 mm, but that of macroaggregates fractions from severely eroded Ultisols decreased with increasing in particle sizes. The percentages of >0.25 mm WSA correlated well with the OM contents of eroded Ultisols ( r 2 = 0.6573, n = 19). The OM contents of macroaggregates in eroded soils showed high correlation with that of the bulk soil, and the correlation coefficients decreased in the order of slightly > moderately > severely eroded Ultisols.

Electro-osmotic chemical treatment is an innovative method to improve the strength of soft clays for geotechnical engineering purposes; the effectiveness of the treatment may be related to treatment time, the concentration of the solutions injected, and to variation of pH in the clay. The objective of this study was to investigate the relationship between the above-mentioned factors and the improvement in strength when calcium chloride solution was used as an injection material. A series of tests was carried out by injecting different concentrations of calcium chloride solution into a kaolin suspension, for different treatment times, during electro-osmosis. After the tests, the pH, cone resistance, water content, and concentration of Ca 2+ in the kaolin at different locations were measured and analyzed. The results show that the concentration of Ca 2+ in the kaolin, the pH, and the strength were increased near the cathode with increases in concentration of CaCl 2 and treatment time. An insignificant increase in strength, due to ion exchange over the entire specimen, for short treatment times of 2 to 24 h, was observed because of a small increase in concentration of Ca 2+ and in pH. During long-term treatment (120 h), a considerable increase in concentration of Ca 2+ (137.0 mg/g) and pH (pH = 10) was observed near the cathode. This led to a pozzolanic reaction, which in turn caused a significant increase in the mechanical strength of the kaolin.