Enhancement of volatile fatty acids production from rice straw via anaerobic digestion with chemical pretreatment.

Rice straw is one of the most abundant renewable biomass sources and was selected as the feedstock for the production of volatile fatty acids (VFAs) from which microbial biodiesel can be produced. Two kinds of chemical pretreatments involving nitric acid and sodium hydroxide were investigated at 150 °C with 20 min of reaction time. The nitric acid pretreatment generated the most hemicellulose hydrolyzate, while significant reduction of the lignin occurred with sodium hydroxide pretreatment. Anaerobic digestion of 20 g/L rice straw yielded 6.00 and 7.09 g VFAs/L with 0.5% HNO3 and 2% NaOH, respectively. The VFAs yield with 2% NaOH was 0.35 g/g.

A comparative study on the Cs adsorption/desorption and structural changes in different clay minerals.

We investigated the structural changes in clay minerals after Cs adsorption and understood their low desorption efficiency using an ion-exchanger. We focused on the role of interlayers in Cs adsorption and desorption in 2:1 clay minerals, namely illite, hydrobiotite, and montmorillonite, using batch experiments and XRD and EXAFS analyses. The adsorption characteristics of the clay minerals were analyzed using cation exchange capacity (CEC), maximum adsorption isotherms (Qmax), and radiocesium interception potential (RIP) experiments. Although illite showed a low CEC value, it exhibited high selectivity for Cs with a relatively high RIP/CEC ratio. The Cs desorption efficiency after treatment with a NaCl ion exchanger was the highest for illite (74.3%), followed by hydrobiotite (45.5%) and montmorillonite (30.3%); thus, Cs adsorbed onto planar sites, rather than on interlayers or frayed edge sites (FESs), is easily desorbed. After NaCl treatment, XRD analysis showed that the low desorption efficiency was due to the collapse of the interlayer-fixed Cs, which tightly narrowed the interlayers' hydrobiotite due to the ion exchange of divalent cations (Mg2+ or Ca2+) into the monovalent cation (Na+). Moreover, EXAFS analysis showed that hydrobiotite formed inner-sphere structures after NaCl desorption, indicating that it was difficult to remove Cs from NaCl desorption due to the collapsed hydrobiotite and montmorillonite interlayers as well as the strong bonding in FESs of illite. In contrast, chelation desorption using oxalic acid effectively dissolved the narrowed interlayers of hydrobiotite (98%) and montmorillonite (85.26%), enhancing the desorption efficiency. Therefore, low desorption efficiency for Cs clays using an ion exchanger was caused by the collapsed interlayer due to the exchange between monovalent cation and divalent cation.

Magnetic hierarchical titanium ferrocyanide for the highly efficient and selective removal of radioactive cesium from water.

Selective adsorption is the most suitable technique for eliminating trace amounts of 137Cs from various volumes of 137Cs-contaminated water, including seawater. Although various metal ferrocyanide (MFC)-functionalized magnetic adsorbents have been developed for the selective removal of 137Cs and magnetic recovery of adsorbents, their adsorption capacity for Cs remains low. Here, magnetic hierarchical titanium ferrocyanide (mh-TiFC) was synthesized for the first time for enhanced Cs adsorption. Hierarchical TiFC, comprising 2-dimensional TiFC flakes, was synthesized on SiO2-coated magnetic Fe3O4 particles using a sacrificial TiO2 shell as a source of Ti4+ via a reaction with ferrocyanide under acidic conditions. The resultant mh-TiFC exhibited the highest maximum adsorption capacity (434.8 mg g-1) and enhanced Cs selectivity with an excellent Kd value (6,850,000 mL g-1) compared to those of previously reported magnetic Cs adsorbents. This enhancement was attributed to the hierarchical structure, which reduced intracrystalline diffusion and increased the surface area available for direct Cs adsorption. Additionally, mh-TiFC (0.1 g L-1) demonstrated an excellent removal efficiency of 137Cs exceeding 99.85% for groundwater and seawater containing approximately 22 ppt 137Cs. Therefore, mh-TiFC offers promising applications for the treatment of 137Cs-contaminated water.

Evaluation of derived concentration guideline levels reflecting the site-specific data for the soil of the Korea research reactor unit 1 and 2.

The purpose of this study is to evaluate the derived concentration guideline levels for unrestricted site reuse the Korea research reactor unit 1 and 2. Distribution coefficients for Co-60 and Sr-90 were derived, and site-specific values of the KRR soil were applied for the DCGLs for the seven target nuclide. The distribution coefficients of Co-60 and Sr-90 were 6,128 and 86.0 mL/g. The DCGLs derived from the dose by age group were 0.053 Bq/g for Co-60 and 45.0 Bq/g for H-3.

Enhanced removal of cesium from hydrobiotite using polyacrylonitrile (PAN)-based nickel ferrocyanide beads.

The desorption of cesium (Cs) from contaminated clay minerals remains challenging because of the restricted efficiency of the removal process. Therefore, in the present study, a bead-type adsorbent was added during the conventional acid washing process to improve the removal of Cs+ from a clay mineral. As the Cs+ adsorbent, polyacrylonitrile-based nickel potassium hexacyanoferrate (NiFC-PAN) was used to selectively adsorb Cs+ in a strongly acidic solution containing competing ions. To prevent erosion of the adsorbent under harsh environmental conditions and to facilitate the separation of clay particles, PAN was deliberately constructed as large beads. The synthesized adsorbent (NiFC/PAN in a 2:1 ratio) showed high selectivity for Cs+, with a maximum capacity for Cs+ adsorption of 162.78 mg/g in 0.5 M HNO3 solution. Because the NiFC-PAN demonstrated greater Cs+ selectivity than the clay mineral (hydrobiotite, HBT), the addition of NiFC-PAN during the acid washing significantly increased Cs+ desorption (73.3%) by inhibiting the re-adsorption of Cs+ on the HBT. The radioactivity of 137Cs-HBT was substantially decreased from 209 to 27 Bq/g by the acid treatment in the presence of NiFC-PAN, corresponding to a desorption efficiency of 87.1%. Therefore, these results suggest that the proposed technique is a potentially useful and effective method for decontamination of radioactive clay.

Post-substitution of magnesium at CaI of nano-hydroxyapatite surface for highly efficient and selective removal of radioactive 90Sr from groundwater.

We have modified the ion-exchange affinity of nano-Hydroxyapatite (Ca5(PO4)3OH, HAP) surface for the rapid and selective adsorption of 90Sr from groundwater. The modification was achieved by the post-substitution of cations (Na+, Mg2+, Cu2+, Ba2+, Fe3+, and Al3+) for parent Ca2+ within surface structure of HAP. The diffraction patterns of modified HAP showed a slight shift of the (002) peak between 25° and 27° 2θ depending the ionic radius of the substituted cation. Magnesium substituted HAP, Mg-HAP, exhibited the highest removal efficiency (>95%) for 10 ppm of Sr2+, which is attributable to the higher ion-exchange affinity of substituted Mg2+ than parent Ca2+ toward Sr2+. The results of various analyses revealed that Mg substitution dominantly occurred at the CaI site of HAP, which enabled the Mg-HAP to adsorb Sr2+ at both of CaI and CaII sites whereas bare HAP could adsorb Sr2+ mainly at CaII site. Adsorption isotherms and the kinetics of Mg-HAP for Sr2+ were evaluated using a bi-Langmuir isotherm and a pseudo-second-order kinetic model, which demonstrated the Mg-HAP exhibited the highest adsorption capacity (64.69 mg/g) and fastest adsorption kinetics (0.161-1.714 g/(mg·min)) than previously modified HAPs. In the presence of competing cations at circumneutral pHs, the enhanced performance of the Mg-HAP led to a greater than 97% reduction of 90Sr (initial radioactivity = 9500 Bq/L) within 1 h. The distribution coefficient of Mg-HAP was 1.3-6.6 × 103 mL/g while that of bare HAP was 1.2-6.6 × 102 mL/g. The findings in the present study highlight that the ion-exchange affinity of CaI and CaII sites on HAP surface plays a key-role in 90Sr uptake. The proposed modification method can simply increase the affinity of HAP surface, therefore, this work can further improve the deployment of an in situ remediation technology for 90Sr contaminated groundwater, i.e., Mg-HAP-based permeable reactive barrier.

Cesium Removal from Nonexpandable Illite Clay by Chloride Salt Treatment.

Extracting cesium (Cs) from nonexpandable illite clay is important in the remediation of radioactive Cs-contaminated soil. In this study, we investigated a chloride salt treatment technique for the removal of Cs from illite. Cs-loaded illite samples with initial Cs concentrations of 2430 and 690 ppm were treated using a NaCl-MgCl2-CaCl2 ternary salt system at 400-850 °C under ambient pressure to suppress Cs loss by vaporization. As a result of the treatment at 850 °C, wherein the salt was in a molten state, the Cs concentration was reduced by 99.5% (to 11.6 ppm) in the first sample and by 99.4% (to 3.86 ppm) in the second sample. Cs removal was achieved for these two samples even in a solid-state reaction at 400 °C, with reductions of 83.3% (407 ppm) and 73.3% (184 ppm), respectively. CsCl was formed by the reaction and remained stable in the salt. The incorporation of cations from the salt (mainly Mg2+) to illite induced structural evolution forming an indialite phase to expel Cs from the clay samples.

Characteristic and remediation of radioactive soil in nuclear facility sites: a critical review.

A huge amount of radioactive soil has been generated through decommissioning of nuclear facilities around the world. This review focuses on the difficulties and complexities associated with the remediation of radioactive soils at the site level; therefore, laboratory studies were excluded from this review. The problems faced while remediating radioactive soils using techniques based on strategies such as dry separation, soil washing, flotation separation, thermal desorption, electrokinetic remediation, and phytoremediation are discussed, along with appropriate examples. Various factors such as soil type, particle size, the fraction of fine particles, and radionuclide characteristics that strongly influence radioactive soil decontamination processes are highlighted. In this review, we also survey and compare the pool of available technologies currently being used for the remediation of radionuclide-contaminated soils, as well as the economic aspects of soil remediation using different techniques. This review demonstrates the importance of the integrated role of various factors in determining the effectiveness of the radioactive soil decontamination process.

Sorption behavior of cesium on silt and clay soil fractions.

The effect of clay mineral composition on Cs adsorption behavior of silt and clay fractions (SC-fractions) of soil was investigated. Surface soil samples were collected within 2 km of Kori and Wolsong nuclear power plants in South Korea, and SC-fractions (<20 µm) were separated. The physicochemical properties of SC-fractions and types of clay minerals contained in the SC-fractions were analyzed. The cesium adsorption capacity of the SC-fractions, and affinity between the SC-fractions and Cs, were investigated by isothermal adsorption analysis using the dual-site Langmuir adsorption model. To understand selective adsorption of Cs, the radiocesium interception potential and distribution coefficient of the SC-fractions were analyzed in the presence or absence of competing ions. The radiocesium distribution coefficient of the SC-fractions showed a trend similar to that of the Langmuir sorption coefficient of high-affinity binding sites for Cs in the SC-fractions. The SC-fractions of Kori soils that contain only non-expandable clay minerals including highly weathered mica had low Cs adsorption capacity. However, the SC-fractions of Kori soils showed higher Cs adsorption selectivity compared to the SC-fractions of Wolsong soils containing expandable clay minerals and micaceous mineral with a low degree of weathering. It is predicted that the highly weathered micas have high affinity to Cs, and such clay minerals contribute the most to the adsorption process in dilute solutions.

Application of polyethylenimine-coated magnetic nanocomposites for the selective separation of Cs-enriched clay particles from radioactive soil.

The separation of Cs-enriched fine particles is a highly effective way to reduce the volume and radioactivity of contaminated soil. This work demonstrated the application of polyethylenimine (PEI)-coated Fe3O4 nanocomposites and a mesh filter for the selective separation of clay particles from Cs-contaminated soil. The PEI coating on the Fe3O4 nanoparticles enhanced the binding force between the magnetic nanoparticles and clay minerals via electrostatic attraction; thus, approximately 100% of the clay particles were magnetically separated from solution by Fe3O4-PEI nanocomposites at a low dose (0.04 g-nanocomposite per g-clay). In separation experiments with soil mixtures, clay- and silt-sized fine particles that had been magnetized by Fe3O4-PEI nanocomposites were selectively separated, and the separation efficiency improved when a mesh filter was added to exclude physically large particles. The combination of magnetic and sieving separation thoroughly separated fine particles from soil by reducing the volume of the magnetic fraction. We also evaluated the magnetic-sieving separation method for the selective removal of clay particles from 137Cs-contaminated soil. The decrease in radioactivity in the treated nonmagnetic fraction, which accounted for 87.5% of the total soil, corresponded to a high decontamination efficiency of approximately 90%. The developed separation technology offers great potential for the efficient remediation of radioactive soil.

Selective separation of Cs-contaminated clay from soil using polyethylenimine-coated magnetic nanoparticles.

We evaluated the feasibility of using magnetic nanoparticles (MNPs) coated with polyethylenimine (PEI), a cationic polymer, to remediate radioactive contaminated soil by separating Cs-contaminated clay from the soil. The influences of the solution pH, PEI-to-MNPs mass ratio, and the PEI-MNPs dose on the magnetic separation performance were systematically examined. The highest SE% of illite from solution through electrostatic attraction was approximately 100% at a mass ratio of 0.04 g-PEI-MNPs/g-clay. The PEI coating clearly enhanced the adhesion between MNPs and clay minerals by increasing the quantity of functional amine groups available for adsorbing negatively charged clay minerals. In separation experiments using a soil mixture, the PEI-coated MNPs selectively separated clay- and silt-sized fine particles smaller than 0.038 mm even in the presence of a large amount of sand when used at a low dose (mass ratio of 0.05 g-PEI-MNPs/g-clay) and without pH control. We also used the PEI-MNPs to separate 137Cs-contaminated illite from soil under an external magnetic field. After magnetic separation, the highest removal efficiency achieved for 137Cs removal from the treated soil was 81.7% at a low nanoparticle dosage, which resulted in satisfying the reduction of radioactivity and waste volume. The results clearly demonstrate that the selective separation of Cs-contaminated clay using PEI-coated MNPs is a promising technique for remediating radioactive soil.

Cs desorption behavior during hydrothermal treatment of illite with oxalic acid.

The desorption of radioactive cesium (Cs) in soil is influenced by the clay mineral type, adsorption site, and concentration of Cs. In this study, experiments to detect desorption of non-radioactive and radioactive Cs from illite using oxalic acid were performed for 2 days at 70 °C in hydrothermal conditions. The results showed that the 133Cs removal efficiency by oxalic acid and inorganic acid treatment was similar at high concentration (22.86 mmol/kg) of non-radioactive 133Cs. In the radioactive 137Cs experiment, the removal efficiency by oxalic acid was higher than that by inorganic acid at low concentration (0.79 × 10-6 mmol/kg) of radioactive 137Cs. Based on the illite hypothetical frayed edge site (FES) concentration of 0.612 mmol/kg, the results suggested that 137Cs was preferentially adsorbed to FES on illite. The 137Cs at low concentration was difficult to remove because it was irreversible adsorption to FES, while the non-radioactive Cs at high concentration was mainly adsorbed to planar sites, and so was easy to desorb by ion exchange. Based on the results of NMR, FTIR, and XPS analyses, we concluded that the higher efficiency of 137Cs removal at low concentration by oxalic acid treatment than by treatment with inorganic acid was because of chelation effects associated with the complexation of oxalic acid (ligands) and metal ions in irreversible site (FES).

Desorption of cesium from hydrobiotite by hydrogen peroxide with divalent cations.

In this study, hydrogen peroxide (H2O2) was used to enhance the cation-exchange treatment for Cs+ desorption from clay minerals. Among various investigated clay minerals, hydrobiotite (HBT), which has interstratified layers of vermiculite and biotite, exhibited the highest Cs+ sorption capacity and the most favorable H2O2 activation because of its high Fe content. In X-ray diffraction analysis, HBT treated with H2O2 and 0.1 M Mg2+ showed substantial changes in its basal spacing, indicating expansion of the interlayer region induced by treatment of H2O2 and strongly hydrated divalent cations. In addition, more than 80% of the Cs+ was readily desorbed from HBT with 35% H2O2 solution and 0.1 M Mg2+ at room temperature. After three cycles under the same treatment conditions (35% H2O2 solution and 0.1 M Mg2+), approximately 99% removal of radioactive Cs+ was achieved. These results suggested that H2O2 treatment with solvated Mg2+ enhanced Cs+ desorption from HBT by altering the interlayer region through intercalation of hydrated divalent cations in conjunction with the H2O2 decomposition reaction.

Enhanced removal of cesium by potassium-starved microalga, Desmodesmus armatus SCK, under photoheterotrophic condition with magnetic separation.

This study investigated the feasibility of using photoheterotrophic microalga, Desmodesmus armatus SCK, for removal of cesium (Cs+) followed by recovery process using magnetic nanoparticles. The comparison of three microalgae results indicated that D. armatus SCK removed the most Cs+ at both 25 °C and 10 °C. The results also revealed that the use of microalga grown in potassium (K+)-starved condition improves the accumulation of Cs+. Heterotrophic mode with addition of volatile fatty acids (VFAs), especially acetic acids (HAc), also enhanced removal of Cs+ by K+-starved D. armatus SCK; maximum removal efficiency of Cs+ was almost 2-fold higher than that of cells grown without organic carbon source. The Cs+ taken up by this microalga was efficiently harvested using magnetic nanoparticles, polydiallyldimethylammonium (PDDA)-FeO3. Finally, this strain eliminated more than 99% of radioactive 137Cs from solutions of 10, 100, and 1000 Bq mL-1. Therefore, use of K+-starved microalga, D. armatus SCK, with VFAs could be promising means to remove the Cs from the liquid wastes.

Co-production of biodiesel and alginate from Laminaria japonica.

A process to produce both biodiesel and alginate in an integrated manner from a brown seaweed, Laminaria japonica, was established. Mannitol, a major carbon constituent in L. japonica, served to produce neutral lipids via the heterotrophic cultivation of an oleaginous yeast, Cryptococcus sp.; and simultaneously alginate, a high value product, was extracted to enhance the economic feasibility of the entire process. Only autoclave pretreatment, without need of any chemical agents, was enough to recover all the essential nutrients for the yeast cultivation. Specifically, it could recover 6.4 g L-1 of mannitol to a degree comparable to 6.6 g L-1 obtained by acid-aided pretreatment using 1.5% (v/v) of H2SO4. Maximum fatty acids methyl esters (FAME) content was 30.37% with FAME productivity of 0.56 g L-1 d-1, and the produced FAME could meet the biodiesel quality standards. Na2CO3-based method showed the best efficiency of alginate recovery, yielding 21.06% (w/w). This study supports that L. japonica can indeed be a promising low-cost feedstock for biodiesel production, and it is more so when a high-value product alginate is co-produced.

Removal of radioactive cesium from an aqueous solution via bioaccumulation by microalgae and magnetic separation.

We evaluated the potential sequestration of cesium (Cs+) by microalgae under heterotrophic growth conditions in an attempt to ultimately develop a system for treatment of radioactive wastewater. Thus, we examined the effects of initial Cs+ concentration (100-500 µM), pH (5-9), K+ and Na+ concentrations (0-20 mg/L), and different organic carbon sources (acetate, glycerol, glucose) on Cs+ removal. Our initial comparison of nine microalgae indicated that Desmodesmus armatus SCK had removed the most Cs+ under various environmental conditions. Addition of organic substrates significantly enhanced Cs+ uptake by D. armatus, even in the presence of a competitive cation (K+). We also applied magnetic nanoparticles coated with a cationic polymer (polyethylenimine) to separate 137Cs-containing microalgal biomass under a magnetic field. Our technique of combining bioaccumulation and magnetic separation successfully removed more than 90% of the radioactive 137Cs from an aqueous medium. These results clearly demonstrate that the method described here is a promising bioremediation technique for treatment of radioactive liquid waste.

Development of practical decontamination process for the removal of uranium from gravel.

In this study, a practical decontamination process was developed to remove uranium from gravel using a soil washing method. The effects of critical parameters including particle size, H2SO4 concentration, temperature, and reaction time on uranium removal were evaluated. The optimal condition for two-stage washing of gravel was found to be particle size of 1-2 mm, 1.0 M H2SO4, temperature of 60°C, and reaction time of 3 h, which satisfied the required uranium concentration for self-disposal. Furthermore, most of the extracted uranium was removed from the waste solution by precipitation, implying that the treated solution can be reused as washing solution. These results clearly demonstrated that our proposed process can be indeed a practical technique to decontaminate uranium-polluted gravel.

Hydrodynamic cavitation as a novel pretreatment approach for bioethanol production from reed.

In this study, hydrodynamic cavitation (HC) was employed as a physical means to improve alkaline pretreatment of reed. The HC-assisted alkaline pretreatment was undertaken to evaluate the influence of NaOH concentration (1-5%), solid-to-liquid ratio (5-15%), and reaction time (20-60 min) on glucose yield. The optimal condition was found to be 3.0% NaOH at solid-to-liquid (S/L) ratio of 11.8% for 41.1 min, which resulted in the maximum glucose yield of 326.5 g/kg biomass. Furthermore, simultaneous saccharification and fermentation (SSF) was conducted to assess the ethanol production. An ethanol concentration of 25.9 g/L and ethanol yield of 90% were achieved using batch SSF. These results clearly demonstrated HC system can be indeed a promising pretreatment tool for lignocellulosic bioethanol production.

Effects of ammonium carbonate pretreatment on the enzymatic digestibility and structural features of rice straw.

Rice straw was pretreated with ammonium carbonate ((NH4)2CO3), a major intermediate of ammonia-based carbon capture process, and evaluated for the effects of critical pretreatment parameters including (NH4)2CO3 concentration (5-25%), temperature (60-90°C), and reaction time (4-24 h) on enzymatic digestibility. Pretreatment of rice straw at 80°C for 12 h using 20% (NH4)2CO3 and 1:10 solid to liquid ratio resulted in enzymatic digestibility of 72.2%, which was higher than that pretreated with the same moles of aqueous ammonia. We also investigated physical characteristics of pretreated rice straw, including surface area, pore volume and size, crystallinity, and scanning electron microscopy image. The ammonium carbonate pretreatment process, as a novel pretreatment technique, enhanced enzymatic hydrolysis of lignocellulose by altering structural features.

Enhanced glucose yield and structural characterization of corn stover by sodium carbonate pretreatment.

Na2CO3 was employed as an efficient yet cheap alkaline catalyst for the pretreatment of corn stover. To systematically obtain an optimal condition, the effects of critical pretreatment parameters including Na2CO3 concentration (2-6%), temperature (120-160 °C), and reaction time (10-30 min) on glucose yield were evaluated in lab-scale using response surface methodology. The best conditions were found to be Na2CO3 of 4.1%, temperature of 142.6 °C, and reaction time of 18.0 min, under which glucose yield reached to 267.5 g/kg biomass. Physical properties, based on scanning electron microscopy (SEM) imagery, surface area, pore volume and size, and crystallinity of pretreated corn stover, were examined. The Na2CO3 pretreatment apparently damaged the surface and altered structural features of corn stover, which resulted in the enhancement of enzymatic of hydrolysis. These results evidently support that Na2CO3 is indeed a robust and feasible catalyst for pretreating lignocellulosic biomass.