Methods to Improve nZVI Adsorbance on Silicates Surface for Nitrate Reduction

<p>Efforts to remove excess nitrate in the groundwater typically involves expensive ion-exchange membranes or slow reacting bio-reactors. Nano-sized zero valent iron (nZVI) has been used successfully to reduce nitrate into ammonia in various sites in USA and Europe. However, nZVI has a number of major setbacks associated with it, namely the tendency to agglomerate due to magnetic properties, and the possible toxicity due to the nano-sized material. To circumvent these two setbacks, nZVI could be adsorbed onto solid support. In this research, geothermal sediment microsilicate 600 (Misi) was utilised as a support. Initial results suggested that Misi has potential as a support for nZVI, however modifications were required to improve the adsorbance of nZVI onto Misi surface. Calcination, activation, acid wash and iron oxyhydroxide coating were used as surface modifications for Misi. It was found that the two most important modifications for nZVI adsorption was calcination at either 400 or 600 °C and acid washing in 5.6 M HCl. Equipped with this knowledge, other silica and silicates were also used to adsorb nZVI. For pure silica surfaces, 3-APTES and 3-TPTMS ligands and pore enlarging methods of calcination of porogen and salt wash were also used. nZVI was not able to be fully adsorbed on pure silica surfaces. Four other silicates were examined: Rice husk ash, Western Australia silica fume, Mt Piper fly ash, and precipitated aluminium silicate. Of these, only Western Australia silica fume and precipitated aluminium silicate showed potential as nZVI support. Based on the SEM-EDS XRD data of all the silica and silicates, it could be tentatively concluded that nZVI requires an aluminium silicate surface for successful adsorption. Aluminium silicate surfaces typically has an exchangeable cation present, and this cation might play a part in nZVI adsorption. The nZVI/Misi surface was then utilised to reduce nitrate. It was discovered that even though activation and FeOOH did not play a part in nZVI adsorption onto Misi surface, these two steps were important in reduction of nitrate, as the presence of activation and FeOOH increase the reduction of nitrate significantly within 60 minutes. The Misi-supported nZVI were also shown to be more stable in dispersion, and less agglomerated as shown in a sand column experiment.</p>

Methods to Improve nZVI Adsorbance on Silicates Surface for Nitrate Reduction

<p>Efforts to remove excess nitrate in the groundwater typically involves expensive ion-exchange membranes or slow reacting bio-reactors. Nano-sized zero valent iron (nZVI) has been used successfully to reduce nitrate into ammonia in various sites in USA and Europe. However, nZVI has a number of major setbacks associated with it, namely the tendency to agglomerate due to magnetic properties, and the possible toxicity due to the nano-sized material. To circumvent these two setbacks, nZVI could be adsorbed onto solid support. In this research, geothermal sediment microsilicate 600 (Misi) was utilised as a support. Initial results suggested that Misi has potential as a support for nZVI, however modifications were required to improve the adsorbance of nZVI onto Misi surface. Calcination, activation, acid wash and iron oxyhydroxide coating were used as surface modifications for Misi. It was found that the two most important modifications for nZVI adsorption was calcination at either 400 or 600 °C and acid washing in 5.6 M HCl. Equipped with this knowledge, other silica and silicates were also used to adsorb nZVI. For pure silica surfaces, 3-APTES and 3-TPTMS ligands and pore enlarging methods of calcination of porogen and salt wash were also used. nZVI was not able to be fully adsorbed on pure silica surfaces. Four other silicates were examined: Rice husk ash, Western Australia silica fume, Mt Piper fly ash, and precipitated aluminium silicate. Of these, only Western Australia silica fume and precipitated aluminium silicate showed potential as nZVI support. Based on the SEM-EDS XRD data of all the silica and silicates, it could be tentatively concluded that nZVI requires an aluminium silicate surface for successful adsorption. Aluminium silicate surfaces typically has an exchangeable cation present, and this cation might play a part in nZVI adsorption. The nZVI/Misi surface was then utilised to reduce nitrate. It was discovered that even though activation and FeOOH did not play a part in nZVI adsorption onto Misi surface, these two steps were important in reduction of nitrate, as the presence of activation and FeOOH increase the reduction of nitrate significantly within 60 minutes. The Misi-supported nZVI were also shown to be more stable in dispersion, and less agglomerated as shown in a sand column experiment.</p>

Discussion of parameters used to distinguish suitable from less suitable HLRW bentonites

Bentonites will be used in the construction of some high-level radioactive waste (HLRW) repositories mostly in combination with crystalline host rocks. They will be used both as a geotechnical barrier (compacted bentonite blocks) around the canisters and for backfilling. The bentonite should be stable in contact with cement pore water, minimize metal corrosion, be stable against erosion and various salt solutions, retard radionuclides, prevent canister displacement, possess high thermal conductivity, be stable against radioactive radiation, keep its swelling capacity even when dried, and, most importantly, should have a low hydraulic conductivity. Bentonites are natural materials (clays) which are dominated by swelling clay minerals called smectites. All bentonites, therefore, possess high water uptake capacity, swelling, and cation exchange properties. Different bentonites from different deposits worldwide differ with respect to their chemical and mineralogical composition, composition and charge distribution of the smectites, particle size and morphology, microstructure (arrangement of particles relative to each other), and interlayer population. All these parameters affect the performances of bentonites in different applications. The bentonite industry, therefore, compares different bentonites based on empirical investigations to produce superior products. Specifications which could be used to select a suitable HLRW bentonite were discussed by Kaufhold and Dohrmann (2016). Additional information has been published later (Kaufhold et al., 2020a, b). First of all, some of the above listed desired bentonite properties depend more on the degree to which it is compacted compared to the natural variability. High compaction decreases the hydraulic conductivity and increases thermal conductivity. In order to prevent canister displacement only a small swelling pressure is needed which is easily achieved by compaction with all bentonites. Generally, the type of exchangeable cation is the most important parameter determining bentonite properties such as swelling and rheology. Large scale deposition tests, however, proved that the cation population will readily equilibrate with the surrounding water. The initial type of exchangeable cation is, therefore, less relevant. More important is the Fe content which negatively affects the thermal and chemical stability. Structural Fe of the smectites can be reduced or oxidized by bacteria and radiation. The Fe content of the bentonite should therefore be low. Highly charged smectites proved to be less corrosive in combination with iron canisters because they provide more reducing conditions compared to low charged ones. Bentonites containing highly charged smectites should be preferred if Fe canisters are used. In the case of Cu canisters no effect of the charge could be found. Also, soluble or at least partly soluble components such as sulphates, sulphides, carbonates, and organic matter should be absent since their possible dissolution would decrease the dry density and hence the swelling pressure. The presence of reactive silica in some bentonites proved to buffer the dissolution reactions at the cement bentonite interface and hence could have a beneficial effect.

Diagnostic Assessment and Restoration Plan for Damaged Forest around the Seokpo Zinc Smelter, Central Eastern Korea

Research Highlights: This study was carried out to diagnose the forest ecosystem damaged by air pollution and to then develop a restoration plan to be used in the future. The restoration plan was prepared by combining the diagnostic assessment for the damaged forest ecosystem and the reference information obtained from the conservation reserve with an intact forest ecosystem. The restoration plan includes the method for the amelioration of the acidified soil and the plant species to be introduced for restoration of the damaged vegetation depending on the degree of damage. Background and Objectives: The forest ecosystem around the Seokpo smelter was so severely damaged that denuded lands without any vegetation appear, and landslides continue. Therefore, restoration actions are urgently required to prevent more land degradation. This study aims to prepare the restoration plan. Materials and Methods: The diagnostic evaluation was carried out through satellite image analysis and field surveys for vegetation damage and soil acidification. The reference information was obtained from the intact natural forest ecosystem. Results: Vegetation damage was severe near the pollution source and showed a reducing trend as it moved away. The more severe the vegetation damage, the more acidic the soil was, and thereby the exchangeable cation content and vegetation damage were significantly correlated. The restoration plan was prepared by proposing a soil amelioration method and the plants to be introduced. The soil amelioration method focuses on ameliorating acidified soil and supplementing insufficient nutrients. The plants to be introduced for restoring the damaged forest ecosystem were prepared by compiling the reference information, the plants tolerant to the polluted environment, and the early successional species. The restoration plan proposed the Pinus densiflora, Quercus mongolica, and Cornuscontroversa–Juglansmandshurica communities as the reference conditions for the ridge, slope, and valley, respectively, by reflecting the topographic condition. Conclusions: The result of a diagnostic assessment showed that ecological restoration is required urgently as vegetation damage and soil acidification are very severe. The restoration plan was prepared by compiling the results of these diagnostic assessments and reference information collected from intact natural forests. The restoration plan was prepared in the two directions of soil amelioration and vegetation restoration.

EVALUATION OF NUTRIENT STOCKS AND SOME SOIL INDICES OF AGRO-ECOSYSTEM AS AFFECTED BY LONG-TERM MONOCROPPING SYSTEM

Objectives: This study investigates nutrients stock and some soil indices of agro-ecosystem soil as affected by monoculture cropping system (cacao plantation). This was with a view to provide comprehensive understanding of soil nutrient dynamics in the ecosystems due to their different management practices. Methods: The study was carried out in 0.063 ha sample plots, three each in natural forests and cacao plantations adjacent to each other. In each plot, five core soil samples were randomly collected at two depths (0–15 and 15–30 cm), bulked according to depth, air-dried, sieved through 2 mm sieve, and analyzed for soil physicochemical properties using standard methods. One-way analysis of variance was used to test significant mean differences of the soil properties among cacao plantation and natural forest at probability level (p≤0.05) at different soil depth. Results: The results showed that soil physical properties such as particle size distribution, moisture contents, and bulk density; chemical properties such as pH, exchangeable cation, organic carbon, organic matter, phosphorus, and sulfur from natural forest were higher than the soil properties in cacao plantation for both top and subsoil. Soil indices such as soil structural stability index, base saturation percentage, and sodium adsorption ratio were higher in natural forest ecosystem than the soil indices of cacao plantation. Conclusion: From this study, it can be concluded that long-term monoculture cropping system had significant effect on nutrients stock and soil indices. This subsequently might result in permanent soil degradation and productivity.

Liming impacts barley yield over a wide concentration range of soil exchangeable cations

Liming has widespread and significant impacts on soil processes and crop responses. The aim of this study was to describe the relationships between exchangeable cation concentrations in soil and the relative yield of spring barley. The hypothesis was that yield is restricted by the concentration of a single exchangeable cation in the soil. For simplicity, we focused on spring barley which was grown in nine years of a long-term experiment at two sites (Rothamsted and Woburn). Four liming rates were applied and in each year the relative yield (RY) and the concentrations of exchangeable cations were assessed. Liming had highly significant effects on the concentrations of most exchangeable cations, except for Cu and K. There were significant negative relationships (either linear or exponential) between the exchangeable concentrations of Mn, Cd, Cr, Al, Fe, Cu, Co, Zn and Ni in soil and soil pH. The relationships between RY and the concentrations of selected exchangeable cations (Mn, Ca and Al) were described well using log-logistic relationships. For these cations a significant site effect was probably due to fundamental differences in soil properties. At both sites the concentrations of exchangeable soil Al were excessive (> 7.5 mg kg−1) and were most likely responsible for reduced barley yields (where RY ≤ 0.5) with soil acidification. At Rothamsted barley yield was non-limited (where RY ≥ 1) at soil exchangeable Mn concentrations (up to 417 mg kg−1) greater than previously considered toxic, which requires further evaluation of critical Mn concentrations.

Effect of Exchangeable Cation in Clays on the Yield and Quality of the Bio-Oil during Microwave Pyrolysis of Cellulose

Bio-oil (pyrolysis oil) is an essential feedstock for the production of renewable fossil-free fuels and valuable chemicals. Enhancement of the pyrolysis oil yield and its quality are significant challenges for an efficient and sustainable biorefinery. Here, we report the microwave (MW)-assisted noncatalytic pyrolysis of cellulose, as a green and controllable alternative to conventional heating, in the presence of eco-friendly Li-, Na-, K-, Mg-, Ca- and Ba-bentonites. The detailed analysis of the MV heating traces demonstrates that the bentonite MW activity significantly depends on the presence of internal water. The intensity of this interaction is controlled by the cation nature reduced in the order: Li+ > Na+ > K+ and Mg2+ > Ca2+ > Ba2+. A unique experimental design for the MW-assisted pyrolysis of cellulose in the presence of Li-doped clays helps to increase the bio-oil yield to 37.8% with high selectivity towards the commercially useful levoglucosan (purity: 39.36%). The combination of an alternative green heating method and environmentally friendly bentonites can be used many times without recycling. We believe that the improved yields of bio-oil are due to: (i) high MW activity of bentonites, which conventionally increases the heating rates of cellulose; and (ii) production of water by hydrophilic clay minerals, favouring depolymerisation of cellulose.

Distribution of Root-Lesion and Stunt Nematodes, and Their Relationship with Soil Properties and Nematode Fauna in Sugarcane Fields in Okinawa, Japan

Sugarcane cultivation in Japan has not yet focused on suppressing plant-parasitic nematodes. For proper nematode management, it is essential to know the spatial distribution of economically important plant-parasitic nematodes and free-living nematodes that play important roles in terrestrial ecosystems. We aimed to reveal nematode fauna and soil properties in 85 sugarcane fields of three major sugarcane producing islands in Japan, and to examine their relationship by using the mixed-effect model and by visualizing the spatial distributions using the inverse distance weighting (IDW) approach. The nematode community structures were analyzed by non-metric multidimensional scaling (NMDS). Among plant-parasitic nematodes in sugarcane, the root-lesion nematodes (Pratylenchus sp.) and the stunt nematodes (Tylenchorhynchus sp.) were widely distributed in these islands, yet the abundance and the species varied geospatially. Soil pH was significantly correlated with the abundance of Pratylenchus and Tylenchorhynchus species. The abundance of Pratylenchus and Tylenchorhynchus species were significantly correlated with soil pH. The abundance of Pratylenchus was significantly correlated with the abundance of free-living nematodes, the number of free-living nematode species, and exchangeable cation K+, as were the abundance of Tylenchorhynchus to the clay content and that of non-Tylenchorhynchus. This study also revealed that the three islands had different nematode faunas, which were explained especially by soil pH, texture, and exchangeable basic cations.

Stability of Pyruvic Acid Adsorbed Onto Clays and Exposed to Ionizing Radiation: Relevance in Chemical Evolution

Chemical evolution studies focus on the synthesis and stability of organic molecules during various transformative physicochemical processes. Gaining insight into the possible mechanisms behind these processes requires the use of various energy sources and catalysts that can produce such transformations. In this work, ionizing radiation (60Co) was used as a source of energy, and two clays with different exchangeable cations-sodium and iron (III)-were combined with pyruvic acid, a key alpha keto acid in metabolism. The samples of pyruvic acid were prepared at a concentration of 0.01 M; then, adsorption experiments were carried out by combining sodium or iron montmorillonite at different times. The amount that adsorbed onto iron montmorillonite was greater than the amount that adsorbed onto sodium montmorillonite. Samples of alpha keto acid at the same concentration were irradiated-in the absence of clay-at 0 to 146.1 kGy and at two pHs (6.7 and 2.0). The suspended samples with sodium and iron clay were then irradiated at the same doses. The results show that keto acid decomposes more quickly at more acidic pHs. The main reaction to irradiation without clay involves the dimerization of pyruvic acid, and 2,3-dimethyltartaric acid is the majority product. When irradiated in the presence of clay, the main reaction is decarboxylation, and acetic acid is the majority product. The exchangeable cation type modifies the interactions between the organic molecule and the solid phase. The percentage of recovered pyruvic acid is higher for iron montmorillonite than for sodium montmorillonite.