Carbon dioxide-assisted thermochemical conversion of magnetically harvested harmful algae into syngas and metal biochar.

With rising of harmful algae blooming and toxin exposure, practical utilization of harmful algae has been developed. This work aimed to magnetically harvest Microcystis aeruginosa (MA) using iron oxides and investigate the feasibility of algae/iron oxides mixture as feedstock in pyrolytic platform to produce syngas and metal biochar. Carbon dioxide (CO2) was used as a feeding gas to enhance the production efficiency of syngas and also functioned pH controller for better MA harvesting and toxin removal. CO2 support brought multiple benefits: magnetite (Fe3O4) and maghemite (γ-Fe2O3) recovered MA in a relatively short period of time (∼1 min), the recovered biomass generated 34-fold increased carbon monoxide, and metal biochar adsorbed higher amount of toxin from MA (2.8-fold). Pyrolytic utilization of harmful algae supported by CO2 and iron oxides could be one of promising techniques for evolution of metal biochar to remove toxin, while efficiently recover biomass and enhance syngas production.

Adsorption of potentially harmful elements by metal-biochar prepared via Co-pyrolysis of coffee grounds and Nano Fe(III) oxides.

Nano Fe(III) oxide (FO) was used as an amendment material in CO2-assisted pyrolysis of spent coffee grounds (SCG) and its impacts on the syngas (H2 & CO) generation and biochar adsorptive properties were investigated. Amendment of FO led to 153 and 682% increase of H2 and CO in pyrolytic process of SCG, respectively, which is deemed to arise from enhanced thermal cracking of hydrocarbons and oxygen transfer reaction mediated by FO. Incorporation of FO successfully created porous structure in the produced biochar. The adsorption tests revealed that the biochar exhibited bi-functional capability to remove both positively charged Cd(II) and Ni(II), and negatively charged Sb(V). The adsorption of Cd(II) and Ni(II) was hardly deteriorated in the multiple adsorption cycles, and the adsorption of Sb(V) was further enhanced through formation of surface ternary complexes. The overall results demonstrated nano Fe(III) oxide is a promising amendment material in CO2-assisted pyrolysis of lignocellulosic biomass for enhancing syngas generation and producing functional biochar.

Establishment of geochemical thresholds for vanadium throughout Korea and at potential development sites using geochemical map data.

Geochemical maps can be used for a variety of purposes, one of which is to establish regional or local geochemical thresholds for the analyzed elements. In the case of vanadium, as industrial demand and use increase, it is necessary to expand the development of vanadium in Korea. However, the environmental management standards are insufficient. Therefore, in this study, using geochemical data, we derived geochemical threshold values for the entire country and areas with potential for the development of vanadium deposits. The regional (country-wide) threshold value was derived using logarithmic transformation of raw data (N = 23,548) of the first- and second-order stream sediments collected across the country in the late 1990s and the early 2000s. The median + 2 median absolute deviation (MAD) and Tukey inner fence (TIF) values were 116 mg/kg and 200 mg/kg, respectively. Of these, the TIF standard, which showed 0.6% of data exceeding the threshold, was judged to be appropriate for distinguishing clear enrichment or contamination of vanadium. In the case of the Geumsan and Pocheon, areas with potential for vanadium development, the TIF and median + 2 MAD values of 259 mg/kg and 218 mg/kg, respectively, can be used as the criteria for evaluating the impact of environmental pollution before and after deposit development. Likewise, by deriving threshold values of the target elements using geochemical map data, it is possible to provide basic environmental information for geochemical evaluation and follow-up management in advance during large-scale site development.

Fabrication of aluminum beads derived from selectively recovered Al-rich precipitates and their application into defluoridation.

This work introduced a new way of fabricating a granular material with the supply of Al-rich precipitates selectively obtained from acid mine drainage (AMD), and its potential as a promising adsorbent for fluoride (F) was evaluated. Through the selective sequential precipitation (SP) process in the field, Al-rich precipitates with high purity (>81%) were collected at the high recovery rate (>99.8%) as a raw material for adsorbent fabrication. The granular adsorbent (ALB) was synthesized through encapsulation of precipitate powders by chemically inducing polymeric bead formation. The characterization results revealed that ALB possessed a highly porous structure and embedded a large number of nanoparticles of amorphous Al hydroxides inside its framework. Less adsorption of F occurred at an alkaline pH condition due to the competitive effect of hydroxyl ions. The adsorption process can be divided into fast adsorption by the outer surface and slow diffusion in the inner phase. The maximum adsorption capacity of ALB for F was calculated to be 17.7 mg g-1 in the Langmuir isotherm model fitting results. By the repetitive adsorption/desorption and XPS results, it turned out that both chemisorption and physisorption gave a contribution in the removal of F, and the regeneration of adsorbent using NaOH was effective to restore the adsorption capability but accompanied the loss of adsorption sites. As a result, it can be concluded that a granule-type material fabricated using Al-rich precipitates selectively recovered from AMD neutralization can be considered as a promising adsorbent for F removal in aqueous solution.

Zirconia-Assisted Pyrolysis of Coffee Waste in CO2 Environment for the Simultaneous Production of Fuel Gas and Composite Adsorbent.

This work newly employed monoclinic zirconia (ZrO2) as a promoter to improve CO2 pyrolysis of coffee waste (CW). The CO2 pyrolysis of CW presented the high level of CO production (14.3 mol%) during two stages of non-isothermal (280 to 700 °C) and isothermal pyrolysis (kept at 700 °C). At the same condition, the incorporation of ZrO2 improved the CO generation up to about twice that of CW (29.5 mol%) by possibly inducing more conversion of pyrolytic oil into gas. The characterization results exhibited that ZrO2-impregnated biochar (ZrB) possessed the distinctive surface morphology that highly graphitic- and porous carbon layers were covered by ZrO2 nanoparticle clusters. In a series of adsorption experiments, ZrB composite showed pH-dependent As(V) adsorption and pH neutralization ability. The adsorption proceeded relatively rapid with 95% removal during 120 min in the early stage, followed by 5% removal in the remaining 240 min. The maximum adsorption capacity was found to be 25.2 mg g-1 at final pH 8. The reusability and stability of ZrB were demonstrated in the 6 consecutive cycles of adsorption/desorption. As a result, ZrO2-assisted CO2 pyrolysis can potentially produce fuel gas with high CO fraction and composite adsorbent suitable for As(V) removal in acidic wastewater.

Water defluorination using granular composite synthesized via hydrothermal treatment of polyaluminum chloride (PAC) sludge.

In this work, we newly synthesized granular composite (GASA) via hydrothermal treatment of polyaluminum chloride (PAC) and subsequently granulation pelleting with starch gel as an organic binder. The resulting composite was characterized with analytic instruments, and the feasibility of utilizing GASA as adsorbent for the removal of fluoride (F-) was tested in the batch and column experiments. The characterization results revealed that GASA possessed a spherical/porous framework consisting of aluminosilicate (i.e., ordered albite, NaAlSiO3O8). The results of final pH effect experiments and XRD/XPS analyses showed the dominant adsorption mechanisms of F- on GASA were electrostatic attraction by protonated surface Al-OH, ligand exchange between surface hydroxyl groups and F ions, and surface precipitation (i.e., cryolite formation). Based on the results of adsorption kinetics and adsorption isotherm, granulation resulted in the relatively slow kinetics of F adsorption compared to the powder type, but was preferred to retain good adsorption capacity. The regeneration possibility of GASA was also proven with the adsorption/desorption cyclic test. In the column study, 15-cm length of the GASA layer and the flow rate less than 0.85 mL min-1 were proposed to keep the satisfactory level of F in water. The experimental results offer a potential of PAC sludge-derived composite as adsorbent for the removal of F from water.

Pilot-scale passive bioreactors for the treatment of acid mine drainage: efficiency of mushroom compost vs. mixed substrates for metal removal.

Pilot-scale field-testing of passive bioreactors was performed to evaluate the efficiency of a mixture of four substrates (cow manure compost, mushroom compost, sawdust, and rice straw) relative to mushroom compost alone, and of the effect of the Fe/Mn ratio, during the treatment of acid mine drainage (AMD) over a 174-day period. Three 141 L columns, filled with either mushroom compost or the four substrate mixture (in duplicate), were set-up and fed with AMD from a closed mine site, in South Korea, using a 4-day hydraulic retention time. In the former bioreactor, effluent deterioration was observed over 1-2 months, despite the good efficiency predicted by the physicochemical characterization of mushroom compost. Steady state effluent quality was then noted for around 100 days before worsening in AMD source water occurred in response to seasonal variations in precipitation. Such changes in AMD quality resulted in performance deterioration in all reactors followed by a slow recovery toward the end of testing. Both substrates (mushroom compost and mixtures) gave satisfactory performance in neutralizing pH (6.1-7.8). Moreover, the system was able to consistently reduce sulfate from day 49, after the initial leaching out from organic substrates. Metal removal efficiencies were on the order of Al (∼100%) > Fe (68-92%) > Mn (49-61%). Overall, the mixed substrates showed comparable performance to mushroom compost, while yielding better effluent quality upon start-up. The results also indicated mushroom compost could release significant amounts of Mn and sulfate during bioreactor operation.

Water quality changes of a closed underground coal mine in Korea.

The objective of this study was to assess the changes in mine water quality as an underground mine flooded from July 2005 to October 2008. The effect of air injection with a blower into the water was used to evaluate the potential to convert ferrous to ferric iron and to provide in situ treatment and precipitation. Mine flooding averaged 31 cm/day with a linear shape until November 2007, when it flattened out due to outflow. During flooding, mine water pH remained around 6, but Eh shifted from 200 to -150 mV. After the mine water level stabilized, contents of elements such as Fe and SO(4) tended to decrease as time passed. Air was injected by diffusers (150 L/min/each) at three different depths of 2, 3, and 5 m below the water level in the shaft. Dissolved oxygen eventually increased to 4 or 5 mg/L depending on the depth of the diffusers. Aeration caused conversion of ferrous iron to ferric iron and about 30 mg/l of iron was removed from the mine water. Therefore, air injection shows potential as a semi-active treatment or part of conventional treatment to precipitate iron in the mine pool.

Longevity of organic layers of vertical flow ponds for sulfate reduction in treating mine drainages in South Korea.

This study was carried out to evaluate longevity of available organic materials used for sulfate-reducing bacteria (SRB) activity in vertical flow ponds (VFPs) to treat mine drainage in South Korea. Spent mushroom compost samples (SMC) were tested as substrates in VFPs and analyzed for total organic carbon in VFPs, and were collected to analyze total organic carbon (TOC), T-N, T-P, K, metals and residual cellulose to check the longevity assessment. Chemical analysis revealed that the average contents of Fe, Al and Mn in SMC of VFPs were 19,907, 32,137 and 434 mg/kg, respectively. The contents of Fe and Al in SMC of VFPs were much higher than those of the unused SMC (control), but to the contrary, those of Mn showed a reversed tendency. Average TOC content of the controls was 64.19% but in one of the VFP substrates was as low as 15.92%. This might be resulted from SRB consumed the available organic carbon in SMC as VFPs system aged. Contents of T-N in VFPs tended to decrease as VFPs aged. The residual cellulose ranged from 3.88 to 6.72% (g/g). There existed a negative relationship between residual cellulose contents and ages of VFPs. Assuming that SMC in all VFPs had similar compositions when the VFPs were initially established, trend analysis predicted that the amount of carbon source for SRB might be available for 12-15 years further, depending on VFPs.

An engineered cover system for mine tailings using a hardpan layer: a solidification/stabilization method for layer and field performance evaluation.

A cover system for mine tailings with a solidified layer (called an engineered hardpan) was developed in this study to reduce water infiltration, acid generation and sulfide oxidation. Hydrated lime and waterglass were used to produce calcium silicate, which can serve as a binder when constructing a hardpan layer. The compressive strength of each solidified/stabilized material was found to be sufficient in the lab, and the amounts of heavy metals were significantly reduced in chemical leaching tests. Various characteristics of tailings may affect the layer's mechanical strength early on, but a long curing period is capable of compensating for these effects. Heavy metals were stabilized as carbonate-bound phases and sulfide minerals were surrounded by calcium silicate matrix, thereby preventing further reaction. To evaluate the field performance of the system, a hardpan layer was installed on top of tailings on a pilot scale. Leachate with high salt content was generated in the tailings layer in the early stages of monitoring, but after approximately 6 months, the objective was achieved as the hardpan layer gradually stabilized. Notably, during the heavy rainfall season of the later monitoring stage, water infiltration was continuously prevented by the system.

Comparative effectiveness of mixed organic substrates to mushroom compost for treatment of mine drainage in passive bioreactors.

Bioreactors are one possible best sustainable technology to address the mine-impacted water problems. Several prospective substrates (mushroom compost, cow manure, sawdust, wood chips, and cut rice straw) were characterized for their ability to serve as a source of food and energy for sulfate-reducing bacteria. Twenty bench-scale batch bioreactors were then designed and set up to investigate relative effectiveness of various mixtures of substrates to that of mushroom compost, the most commonly used substrate in field bioreactors, for treating mine drainage with acidic (pH 3) and moderate pH (pH 6). Overall, reactive mixtures showed satisfactory performances in generating alkalinity, reducing sulfate and removing metals (Al>Fe>Mn) (up to 100%) at both pH conditions, for all substrates. The mixture of sawdust and cow manure was found as the most effective whereas the mixture containing 40% cut rice straw gave limited efficiency, suggesting organic carbon released from this substrate is not readily available for biodegradation under anaerobic conditions. The mushroom compost-based bioreactors released significant amount of sulfate, which may raise a more concern upon the start-up of field-scale bioreactors. The correlation between the extent of sulfate reduction and dissolved organic carbon/SO(4)(2-) ratio was weak and this indicates that the type of dissolved organic carbon plays a more important role in sulfate reduction than the absolute concentration and that the ratio is not sensitive enough to properly describe the relative effectiveness of substrate mixtures.