Morphology and stability of mineralized carbon influenced by magnesium ions.

Ex situ mineralization of CO2 is a promising technology that employs Ca- and Mg-rich industrial wastes but it simultaneously produces end products. Although Mg is a major mineralization source, it can adversely impact carbonate precipitation and crystal stability during co-precipitation in combination with Ca2+. In this study, the effects of Mg2+ ions on the mineralization process and its products were investigated using precipitates formed at different aqueous concentrations of Mg2+. The final phases of the precipitates were quantitatively evaluated at the end of each process. The alterations undergone by the calcite crystals, which constituted the dominant carbonate phase in each experiment, were analyzed using a sophisticated crystallographic approach. Aragonite was detected at high Mg2+ concentrations (Mg2+/Ca2+ ratio of 2.00), although brucite was the sole phase of the Mg crystal. The increase in Mg2+ ion concentration induced the formation of an amorphous solid. The results revealed that a drastic transformation of the calcite lattice occurred when the ratio of Mg2+/Ca2+ exceeded 1.00, agreeing with the shifts observed in the calcite structure upon comparing the precipitates formed at the Mg2+/Ca2+ ratios of 1.00 and 2.00, wherein microstrain and crystallite sizes changed from 0.040 and 55.33 nm to 0.1533 and 12.35 nm, respectively. At a Mg2+/Ca2+ ratio of 2.00, 6.51% of the Ca2+ ions in the calcite structure were substituted by Mg2+, increasing the surface energy of the crystal and the solubility of the carbonate. Therefore, Mg2+ is a potential hindrance that can impede the precipitation of carbonates and increase instability at certain concentrations.

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.

Setting Behavior and Phase Evolution on Heat Treatment of Metakaolin-Based Geopolymers Containing Calcium Hydroxide.

The setting behavior of geopolymers is affected by the type of source materials, alkali activators, mix formulations, and curing conditions. Calcium hydroxide is known to be an effective additive to shorten the setting period of geopolymers. However, there is still room for improvement in the understanding of the effect of calcium hydroxide on the setting and phase evolution of geopolymers. In this study, the setting behavior and phase evolution of geopolymer containing calcium hydroxide were investigated by XRD analysis. The setting time of the geopolymer was inconsistently shortened as the amount of calcium hydroxide increased. A low calcium hydroxide dose of up to 2% of the total mix weight could contribute to the enhancement of compressive strength of geopolymers besides a fast-setting effect. The C-S-H gel is rapidly precipitated at the early stage of reaction in geopolymers containing high calcium hydroxide with some of the calcium hydroxide remaining intact. The ex-situ high-temperature XRD analysis and Rietveld refinement results revealed that geopolymer and C-S-H gel transformed into Si-rich nepheline and wollastonite, respectively. The wollastonite was also observed in heat-treated geopolymers with a low calcium hydroxide dose. It is believed that C-S-H gel can be precipitated along with geopolymers regardless of how much calcium hydroxide is added.

Comparative Effects of Particle Sizes of Cobalt Nanoparticles to Nine Biological Activities.

The differences in the toxicity of cobalt oxide nanoparticles (Co-NPs) of two different sizes were evaluated in the contexts of the activities of bacterial bioluminescence, xyl-lux gene, enzyme function and biosynthesis of ß-galactosidase, bacterial gene mutation, algal growth, and plant seed germination and root/shoot growth. Each size of Co-NP exhibited a different level of toxicity (sensitivity) in each biological activity. No revertant mutagenic ratio (greater than 2.0) of Salmonella typhimurium TA 98 was observed under the test conditions in the case of gene-mutation experiments. Overall, the inhibitory effects on all five bacterial bioassays were greater than those on algal growth, seed germination, and root growth. However, in all cases, the small Co-NPs showed statistically greater (total average about two times) toxicity than the large Co-NPs, except in shoot growth, which showed no observable inhibition. These findings demonstrate that particle size may be an important physical factor determining the fate of Co-NPs in the environment. Moreover, combinations of results based on various biological activities and physicochemical properties, rather than only a single activity and property, would better facilitate accurate assessment of NPs' toxicity in ecosystems.

Effect of FeS on mercury behavior in mercury-contaminated stream sediment: A case study of Pohang Gumu Creek in South Korea.

This study investigated mercury contamination with respect to the sediment characteristics in Gumu Creek near the Pohang Industrial Complex, South Korea. The contaminated sediment had high levels of Hg, exceeding 250 mg Hg/kg sediment at the sampling position, and high concentrations of iron, sulfur, and organic carbon under extreme anaerobic conditions. The anoxic condition of the sediment produced large amounts of FeS. Hg L3-edge EXAFS analysis revealed that FeS controlled the Hg species in the sediment mainly as ß-HgS like precipitation or Hg-S complexation. We also speculated that the presence of FeS induced the abiotic reduction of Hg(II) to Hg(0) and consequently suppressed the formation of highly toxic methylated mercury species. The results obtained in this study are mostly consistent with those reported in previous studies of geochemical reactions of FeS in controlling Hg(II) under pure FeS mineral systems under laboratory scenarios. This study demonstrates that the laboratory controlled reaction scenarios can explain the field behavior of Hg in the contaminated anoxic sediment of the Gumu Creek site.

Beam-induced redox transformation of arsenic during As K-edge XAS measurements: availability of reducing or oxidizing agents and As speciation.

During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O2 during XAS measurements. With strict O2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

Interaction of Sb(III) with iron sulfide under anoxic conditions: Similarities and differences compared to As(III) interactions.

This study examined the reaction mechanism of arsenite, As(III), and antimonite, Sb(III), with iron sulfide and compared their pH-dependent reaction behaviors under strictly anoxic environments. The comparison of Sb(III) with As(III), based on their chemical similarity, may provide useful insight into understanding the geochemical behavior of the less studied Sb(III). The pH-dependent batch sorption studies revealed that As(III) and Sb(III) displayed similar removal trends with pH in terms of the removal efficiency. However, the aqueous As(III) species transformed to thioarsenite species, while aqueous Sb(III) species remained inert under the highly sulfidic anoxic system. An X-ray absorption spectroscopy study demonstrated the reaction of As(III) and Sb(III) at acidic pH was closely related to the precipitation of sulfide minerals As2S3 and Sb2S3, respectively, as a consequence of the reaction with sulfide produced through mackinawite dissolution. Meanwhile, the removal at basic pH was inferred as a surface reaction, possibly through surface complexation, surface-precipitation, or both. In this study, the pH-dependent Sb(III) uptake mechanisms proved to be similar to the corresponding mechanisms for As(III) uptake, with mackinawite demonstrating a superior capacity to scavenge Sb(III) in ferrous and sulfide-rich reducing environments.

Characterization of iron and manganese minerals and their associated microbiota in different mine sites to reveal the potential interactions of microbiota with mineral formation.

Different environmental conditions such as pH and dissolved elements of mine stream induce precipitation of different minerals and their associated microbial community may vary. Therefore, mine precipitates from various environmental conditions were collected and their associated microbiota were analyzed through metagenomic DNA sequencing. Various Fe and Mn minerals including ferrihydrite, schwertmannite, goethite, birnessite, and Mn-substituted δ-FeOOH (δ-(Fe1-x, Mnx)OOH) were found in the different environmental conditions. The Fe and Mn minerals were enriched with toxic metal(loid)s including As, Cd, Ni and Zn, indicating they can act as scavengers of toxic metal(loid)s in mine streams. Under acidic conditions, Acidobacteria was dominant phylum and Gallionella (Fe oxidizing bacteria) was the predominant genus in these Fe rich environments. Manganese oxidizing bacteria, Hyphomicrobium, was found in birnessite forming environments. Leptolyngbya within Cyanobacteria was found in Fe and Mn oxidizing environments, and might contribute to Fe and Mn oxidation through the production of molecular oxygen. The potential interaction of microbial community with minerals in mine sites can be traced by analysis of microbial community in different Fe and Mn mineral forming environments. Iron and Mn minerals contribute to the removal of toxic metal(loid)s from mine water. Therefore, the understanding characteristics of mine precipitates and their associated microbes helps to develop strategies for the management of contaminated mine water.

Reliability improvement for predicting acid-forming potential of rock samples using static tests.

In predicting the acid-forming potential of rock samples, a combination of acid-base accounting (ABA) and net acid generation (NAG) tests has been commonly used. While simple and economical, this method sometimes shows low reliability such as categorizing certain samples as uncertain (UC). ABA and NAG tests were modified to selectively recover valid minerals in nature and substituted for the original tests. ABA test overestimated acid-producing capacity (in the case of weathered samples) and acid-neutralizing capacity (in the case of plagioclase-including samples) compared to the modified ABA test. NAG test yielded lower NAG pH compared to modified NAG test for samples with high total C content and low total S content. By comparing the correlation coefficients between acid generation amounts by the two evaluation methods, it was confirmed that modified evaluation method (MEM) has a much higher reliability (R 2 = 0.9582) than existing evaluation method (EEM) (R 2 = 0.5873). It was also concluded that exploiting advantages of both EEM and MEM is recommended where EEM is initially applied for general classification and a supplemented static test of MEM is executed for the purpose of correcting the error of UC categorized samples.

Comparison of physicochemical properties between fine (PM2.5) and coarse airborne particles at cold season in Korea.

Although it has been well-known that atmospheric aerosols affect negatively the local air quality, human health, and climate changes, the chemical and physical properties of atmospheric aerosols are not fully understood yet. This study experimentally measured the physiochemical characteristics of fine and coarse aerosol particles at the suburban area to evaluate relative contribution to environmental pollution in consecutive seasons of autumn and winter, 2014-2015, using XRD, SEM-EDX, XNI, ICP-MS, and TOF-SIMS. For these experimental works, the fine and coarse aerosols were collected by the high volume air sampler for 7 days each season. The fine particles contain approximately 10 µg m(-3) of carbonaceous aerosols consisting of 90% organic and 10% elemental carbon. The spherical-shape carbonaceous particles were observed for the coarse samples as well. Interestingly, the coarse particles in winter showed the increased frequency of carbon-rich particles with high contents of heavy metals. These results suggest that, for the cold season, the coarse particles could contribute relatively more to the conveyance of toxic contaminants compared to the fine particles in the study area. However, the fine particles showed acidic properties so that their deposition to surface may cause facilitate the increase of mobility for toxic heavy metals in soil and groundwater environments. The fine and coarse particulate matters, therefore, should be monitored separately with temporal variation to evaluate the impact of atmospheric aerosols to environmental pollution and human health.

Impact of activator type on the immobilisation of lead in fly ash-based geopolymer.

Immobilisation of heavy metals in geopolymers has attracted attention as a potential means of treating toxic wastes. Lead is known to be effectively immobilised in a geopolymer matrix, but detailed explanation for the mechanisms involved and the specific chemical form of lead are not fully understood. To reveal the effect of the activator types on the immobilisation of lead in geopolymers, 0.5 and 1.0wt% lead in the form of lead nitrate was mixed with fly ash and alkaline activators. Different alkaline activators (either combined sodium hydroxide and sodium silicate or sodium aluminate) were used to achieve the target Si:Al ratios 2.0 and 5.0 in geopolymers. Zeolite was formed in aluminate-activated geopolymers having a Si:Al ratio of 2.0, but the zeolite crystallization was suppressed as lead content increased. No specific crystalline phase of lead was detected by X-ray diffraction, electron diffraction or FT-IR spectrometry. In fact, double Cs corrected TEM analysis revealed that lead was evenly distributed with no evidence of formation of a specific lead compound. A sequential extraction procedure for fractionation of lead showed that lead did not exist as an exchangeable ion in geopolymers, regardless of activator type used. Aluminate activation is shown to be superior in the immobilisation of lead because about 99% of extracted lead existed in the oxidizing and residual fractions.

Preparation of Calcined Zirconia-Carbon Composite from Metal Organic Frameworks and Its Application to Adsorption of Crystal Violet and Salicylic Acid.

Zirconia-carbon (ZC) composites were prepared via calcination of Zr-based metal organic frameworks, UiO-66 and amino-functionalized UiO-66, under N2 atmosphere. The prepared composites were characterized using a series of instrumental analyses. The surface area of the ZC composites increased with the increase of calcination temperature, with the formation of a graphite oxide phase observed at 900 °C. The composites were used for adsorptive removal of a dye (crystal violet, CV) and a pharmaceutical and personal care product (salicylic acid, SA). The increase of the calcination temperature resulted in enhanced adsorption capability of the composites toward CV. The composite calcined at 900 °C exhibited a maximum uptake of 243 mg·g-1, which was much greater than that by a commercial activated carbon. The composite was also effective in SA adsorption (102 mg·g-1), and N-functionalization of the composite further enhanced its adsorption capability (109 mg·g-1). CV adsorption was weakly influenced by solution pH, but was more dependent on the surface area and pore volume of the ZC composite. Meanwhile, SA adsorption showed strong pH dependence, which implies an active role of electrostatic interactions in the adsorption process. Base-base repulsion and hydrogen bonding are also suggested to influence the adsorption of CV and SA, especially for the N-functionalized composite.

Benefits of Sealed-Curing on Compressive Strength of Fly Ash-Based Geopolymers.

There is no standardized procedure for producing geopolymers; therefore, many researchers develop their own procedures for mixing and curing to achieve good workability and strength development. The curing scheme adopted is important in achieving maximum performance of resultant geopolymers. In this study, we evaluated the impact of sealed and unsealed curing on mechanical strength of geopolymers. Fly ash-based geopolymers cured in sealed and unsealed moulds clearly revealed that retention of water during curing resulted in superior strength development. The average compressive strength of sealed-cured geopolymers measured after 1 day of curing was a modest 50 MPa, while after 7 day curing the average compressive strength increased to 120~135 MPa. In the unsealed specimens the average compressive strength of geopolymers was lower; ranging from 60 to 90 MPa with a slight increase as the curing period increased. Microcracking caused by dehydration is postulated to cause the strength decrease in the unsealed cured samples. These results show that water is a crucial component for the evolution of high strength three-dimensional cross-linked networks in geopolymers.

Biodegradation of biphenyl and 2-chlorobiphenyl by a Pseudomonas sp. KM-04 isolated from PCBs-contaminated coal mine soil.

The biphenyl-degrading strain, Pseudomonas sp. KM-04, was isolated from polychlorinated biphenyls-contaminated soil sample obtained from the vicinity of a former coal mine. We herein report that strain KM-04 can use biphenyl as a sole carbon source, and resting cells convert biphenyl to its corresponding metabolic intermediates. Incubation of KM-04 with autoclaved mining-contaminated soil for 10 days in a slurry system reduced the levels of biphenyl and 2-chlorobiphenyl by 98.5 % and 82.3 %, respectively. Furthermore, treatment of a mine-soil microcosm with strain KM-04 for 15 days in a composting system under laboratory conditions reduced the levels of biphenyl and 2-chlorobiphenyl by 87.1 % and 68.7 %, respectively. These results suggest that KM-04 is a potential candidate for the biological removal of biphenyl and its chlorinated derivatives from polychlorinated biphenyl-contaminated mining areas.

The effect of granular ferric hydroxide amendment on the reduction of nitrate in groundwater by zero-valent iron.

The feasibility of using granular ferric hydroxide (GFH) with zero-valent iron (Fe(0)) for its potential utility in enhancing nitrate reduction was investigated. The addition of 10gL(-1) GFH to 25gL(-1) Fe(0) significantly enhanced nitrate removal, resulting in 93% removal of 52.2mg-NL(-1) in 36-h as compared to 23% removal with Fe(0) alone. Surface analyses of the reacted Fe(0)/GFH revealed the presence of magnetite on the Fe(0) surface, which probably served as an electron mediator for nitrate reduction. Addition of GFH to Fe(0) also resulted in lower solution pH compared to Fe(0). The rate enhancing effect of GFH on nitrate reduction was attributed to the combined effects of magnetite formation and pH buffering by GFH. GFH amendment (100gL(-1)) significantly increased reduction capacity and longevity of Fe(0) to complete several nitrate reduction cycles before inactivation, giving a total nitrate removal of 205mg-NL(-1), while unamended Fe(0) gave only 20mg-NL(-1) before inactivation during the first reduction cycle. The overall result demonstrated the potential utility of Fe(0)/GFH system that may be developed into a viable technology for removal of nitrate from groundwater.

The role of clay minerals in the reduction of nitrate in groundwater by zero-valent iron.

Bench-scale batch experiments were performed to investigate the feasibility of using different types of clay minerals (bentonite, fuller's earth, and biotite) with zero-valent iron for their potential utility in enhancing nitrate reduction and ammonium control. Kinetics experiments performed with deionized water (DW) and groundwater (GW) revealed nitrate reduction by Fe(0) proceeded at significantly faster rate in GW than in DW, and such a difference was attributed to the formation of green rust in GW. The amendment of the minerals at the dose of 25 g L(-1) in Fe(0) reaction in GW resulted in approximately 41%, 43%, and 33% more removal of nitrate in 64 h reaction for bentonite, fuller's earth, and biotite, respectively, compared to Fe(0) alone reaction. The presumed role of the minerals in the rate enhancement was to provide sites for the formation of surface bound green rust. Bentonite and fuller's earth also effectively removed ammonium produced from nitrate reduction by adsorption, with the removal efficiencies significantly increased with the increase in mineral dose above 5:1 Fe(0) to mineral mass ratio. Such a removal of ammonium was not observed for biotite, presumably due to its lack of swelling property. Equilibrium adsorption experiments indicated bentonite and fuller's earth had maximum ammonium adsorption capacity of 5.6 and 2.1 mg g(-1), respectively.

A simple method for locating the fresh water-salt water interface using pressure data.

Salt water intrusion is a key issue in dealing with exploitation, restoration, and management of fresh ground water in coastal aquifers. Constant monitoring of the fresh water-salt water interface is necessary for proper management of ground water resources. This study presents a simple method to estimate the depth of the fresh water-salt water interface in coastal aquifers using two sets of pressure data obtained from the fresh and saline zones within a single borehole. This method uses the density difference between fresh water and saline water and can practically be used at coastal aquifers that have a relatively sharp fresh water-salt water interface with a thin transition zone. The proposed method was applied to data collected from a coastal aquifer on Jeju Island, Korea, to estimate the variations in the depth of the interface. The interface varied with daily tidal fluctuations and heavy rainfall in the rainy season. The estimated depth of the interface showed a good agreement with the measured electrical conductivity profile.

Arsenic removal using steel manufacturing byproducts as permeable reactive materials in mine tailing containment systems.

Steel manufacturing byproducts were tested as a means of treating mine tailing leachate with a high As concentration. Byproduct materials can be placed in situ as permeable reactive barriers to control the subsurface release of leachate from tailing containment systems. The tested materials had various compositions of elemental Fe, Fe oxides, Ca-Fe oxides and Ca hydroxides typical of different steel manufacturing processes. Among these materials, evaporation cooler dust (ECD), oxygen gas sludge (OGS), basic oxygen furnace slag (BOFS) and to a lesser degree, electrostatic precipitator dust (EPD) effectively removed both As(V) and As(III) during batch experiments. ECD, OGS and BOFS reduced As concentrations to <0.5mg/l from 25mg/l As(V) or As(III) solution in 72 h, exhibiting higher removal capacities than zero-valent iron. High Ca concentrations and alkaline conditions (pH ca. 12) provided by the dissolution of Ca hydroxides may promote the formation of stable, sparingly soluble Ca-As compounds. When initial pH conditions were adjusted to 4, As reduction was enhanced, probably by adsorption onto iron oxides. The elution rate of retained As from OGS and ECD decreased with treatment time, and increasing the residence time in a permeable barrier strategy would be beneficial for the immobilization of As. When applied to real tailing leachate, ECD was found to be the most efficient barrier material to increase pH and to remove As and dissolved metals.