The smectite-illite (SI) reaction is a ubiquitous process in siliciclastic sedimentary environments. For the last 4 decades the importance of smectite to illite (S-I) reaction was described in research papers and reports, as the degree of the (S-I) reaction, termed "smectite illitization", is linked to the exploration of hydrocarbons, and geochemical/petrophysical indicators. The S-I transformation has been thought that the reaction, explained either by layer-by-layer mechanism in the solid state or dissolution/reprecipitation process, was entirely abiotic and to require burial, heat, and time to proceed, however few studies have taken into account the bacterial activity. Recent laboratory studies showed evidence suggesting that the structural ferric iron (Fe(III)) in clay minerals can be reduced by microbial activity and the role of microorganisms is to link organic matter oxidation to metal reduction, resulting in the S-I transformation. In abiotic systems, elevated temperatures are typically used in laboratory experiments to accelerate the smectite to illite reaction in order to compensate for a long geological time in nature. However, in biotic systems, bacteria may catalyze the reaction and elevated temperature or prolonged time may not be necessary. Despite the important role of microbe in S-I reaction, factors that control the reaction mechanism are not clearly addressed yet. This paper, therefore, overviews the current status of microbially mediated smectite-to-illite reaction studies and characterization techniques.
The Shihung mine was restored in the early 90's after abandonment for 20 yews since 1973. Although disposed mine tailings were removed and the site was replaced by an incineration plant, still some residual mine tailings remain in the places including the old mine tailing ditposal area and the adjacent agricultural area. These residual mine tailings are prone to impose an adverse impact on the soil and groundwater and needs investigation for the potential contamination. Mine tailing samples were collected from the old tailing disposal area and the iii paddy. The porewater from the mine tailing were extracted and analysed to investigate chemical changes along the reaction path. Batch leaching tests were also carried out in the laboratory to find any supporting evidence found in the field analysis. Evidence of elemental leaching was confirmed both by the mine tailing and the porewater chemistry in them. The element concentrations of Cu, Cd, Pb, Zn in the porewater exceed the standard for drinking water of Korean government and US EPA. Leaching of heavy metals from the mine tailing seem to be responsible for the contamination. In batch leaching test. heavy metals were either continuous1y released or declined rapidly. Combining the information with porewater variation with depths and the geochemical meodeling results, most of elements are controlled by dissolution and/or precipitation processes, with some solubility controlling solid phases (Cu, Pb, Fe and Zn). Batch leaching test conducted at fixed pH 4 showed much higher releases for the heavy metals up to 400 times (Zn) and this area is becoming more vulnerable to soil and groundwater pollution as precipitation pH shifts to acidic condition.
While most of regulatory communities in abroad recognize ' 'natural attenuation " to include degradation, dispersion, dilution, sorption (including precipitation and transformation), and volatilization as governing Processes, regulators prefer "degradation" because this mechanism destroys the contaminant of concern. Unfortunately, true degradation only applies to organic contaminants and short- lived radionuclides, and leaves most metals and long-lived radionuclides. The natural attenuation Processes may reduce the potential risk Posed by site contaminants in three ways: (i)contaminants could be converted to a less toxic form througy destructive processes such as biodegradation or abiotic transformations; (ii) potential exposure levels may be reduced by lowering concentrations (dilution and dispersion); and (iii) contaminant mobility and bioavailability may be reduced by sorption to geomedia. In this review, authors will focus will focul on "sorption" among the natural attenuation processes of hazardous inorganic contaminants including radionuclides. Note though that sorption and transformation processes of inorganic contaminants in the natural setting could be influenced by biotic activities but our discussion would limit only to geochemical reactions involved in the natural attenuation. All of the geochemical reactions have been studied in-depth by numerous researchers for many years to understand "retardation" process of contaminants in the geomedia. The most common approach for estimating retardation is the determination of distrubution coefficiendts ($K_{d}$) of contaminants using parametric or mechanistic models. As typocally used in fate and contaminant transport calculations such as predictive models of the natural attenuation, the $K_{d}$ is defined as the ratio of the contaminant concentration in the surrounding aqueous solution when the system is at equilibrium. Unfortunately, generic or default $K_{d}$ values can result in significant error when used to predict contaminant migration rate and to select a site remediation alternative. Thus, to input the best $K_{d}$ value in the contaminant transport model, it is essential that important geochemical processes affecting the transport should be identified and understood. Precipitation/dissolution and adsorption/desorption are considered the most important geochemical processes affecting the interaction of inorganic and radionuclide contaminants with geomedia at the near and far field, respectively. Most of contaminants to be discussed in this presentation are relatively immobile, i.e., have very high $K_{d}$ values under natural geochemical environments. Unfortunately, the obvious containment in a source area may not be good enough to qualify as monitored natural attenuation site unless owner demonstrate the efficacy if institutional controls that were put in place to protect potential receptors. In this view, natural attenuation as a remedial alternative for some of sites contaminated by hazardous-inorganic components is regulatory and public acceptance issues rather than scientific issue.
Journal of Korean Society of Environmental Engineers
/
v.22
no.10
/
pp.1747-1756
/
2000
Crab shell particles (Protunus trituberculatus) and activated carbon (Norit 0.8 SUPRA) were used as packing material in a fixed-bed column. When 1 g crab shell was added in the column packed with 10 g activated carbon. breakthrough to influent 10 mg Pb/L occurred at 1520 bed volumes. as compared to 380 bed volumes for 10 g activated carbon only. Addition of crab shell particles into activated carbon column resulted in increased uptake of lead. The dramatic improvement might be attributed to an increase in $co_3{^{2-}}$ and $OH^-$ available for the binding of lead. From the result of analyses, the major mechanism of lead removal was based on dissolution of $CaCO_3$ in the crab shell followed by precipitation of $Pb_3(CO_3)_2(OH)_{2(s)}$ on the surface of activated carbon. The lead uptake increased two fold as the influent lead concentration was increased from 10 to 50 mg/L. However, it decreased by 40% as the influent pH was lowered from 5.0 to 3.0.
Buffer capacities for two Bo horizon soils or Andisols developed from different parent materials have been investigated. The titration curves from column leaching experiment show that buffering occurred at pH 4.0 and 6.0. The buffer intensity or soil developed from pyroclastic materials (P-soil) is higher than that from basalts (B-soil). From batch test we have found that proto-imogolite and/or imogolite may control Al solubility as well as $Al(OH) _3$in the moderate acid condition. The buffer intensities ($\beta$) of P-soils were plotted on the theoretical buffering curve of $Al(OH)_3$, while $\beta$ of B-soils approached to that of proto-imogolite, which shows the solubility of short-range-order materials in P-soil control the buffer capacity. Buffering at pH 6.0 is thought to be the result of dissolution of some silicate clays and exchange reactions between $H^{+ }$and base-forming cations. Considering the amount of annual acid precipitation, aluminum solubility of Andisols, and the low BS (Base Saturation percentage), it can be predicted that prolonged acid precipitation will reduce the buffer capacity of soils and lead to soil acidification.
The effects of RRA treatment on the microstructures and mechanical properties of 7050 Al alloy were investigated by differential scanning calolimetry, transmission electron microscopy, microhardness measurement and electrical conductivity. The hardness of 2nd-step aged specimen at $175^{\circ}C$ was decreased to mimimum value and increased to a peak hardness, and then re-decreased with retrogression treatment. It was found that the hardness of 2nd-step aged specimen was further increased by 3rd step aging treatment($120^{\circ}C$x24h). The initial decrease in hardness during 2nd-step aging was due to the partial dissolution of pre-existing GP zone, the major precipitation hardening phase at T6 condition. It was confirmed that the major precipitation hardening phase at 3rd-step aging was GP zone and η' phase. The electrical conductivity increased continually through 2nd-step and 3rd-step aging treatment. It was conclude that the optium 2nd-step aging condition was at $175^{\circ}C$ for 50min by considering the hardness and electrical conductivity.
The objective of this study was to obtain a better understanding of the delayed hydride cracking (DHC) of Zr-2.5Nb alloy. The DHC model has some defects: first, it cannot explain why the DHC velocity (DHCV) becomes constant regardless of an applied stress intensity factor, even though the stress gradient is affected by the applied stress intensity factor at the notch tip. Second, it cannot explain why the DHCV has a strong dependence on the method of approaching the test temperature by a cool-down or a heating-up, even under the same stress gradient, and third, it cannot predict any hydride size effect on the DHC velocity. The DHC tests were conducted on Zr-2.5Nb compact tension specimens with the test temperatures reached by a heating-up method and a cool-down method. Crack velocities were measured in hydrided specimens, which were cooled from solution-treatment temperatures at different rates by being furnace-cooled, water-quenched, and liquid nitrogen-quenched. The resulting hydride size, morphology, and distributions were examined by optical metallography. It was found that fast cooling rates, which produce very finely dispersed hydrides, result in higher crack growth rates. This different DHC behavior of the Zr-2.5Nb tube with the cooling rate after a homogenization treatment is due to the precipitation of the $\gamma$-hydrides only in the water-quenched Zr-2.5Nb tube. This experiment will provide supporting evidence that the terminal solid solubility of a dissolution (TSSD) of $\gamma$-hydrides is higher than that of $\delta$-hydrides.
This study estimated stabilization efficiency of As and heavy metal contaminated agricultural soil in abandoned mine through pot experiment. Also contaminants uptake of plant (lettuce) was compared as function of amendment (limestone, steelmaking slag and the mixture of these) addition. In soil solution analysis, concentration of contaminants in soil solutions which added limestone or steelmaking slag were lower than that of the mixture. Especially in As analysis, concentration with 5% (wt) addition of steelmaking slag showed the lowest value among those with other amendments. This seems that As stabilization happens through Fe adsorption during precipitation of Fe by pH increasing. Leachability of As in stabilized soil by TCLP was represented similar result with soil solution analysis. However leachability of heavy metals in stabilized soil was similar with that of non-stabilized soil due to dissolution of alkali precipitant by weak acid. Contaminants uptake rate by plant was also lower when limestone or steelmaking slag was used. However this study revealed that concentration of contaminants in soil solution didn't affect to the uptake rate of plant directly. Because lower $R^2$ (coefficient of determination) was represented in linear regression analysis between soil solution and plant.
Precipitation was formed during the preparation of decoction from a mixture of Scutellariae Radix and Coptidis Rhizoma. Baicalin and berberine were identified in this coprecipitated product (CPP) and these components were the active ingredients of two herbal medicine. We extracted respectively crude baicalin and berberine in Scutellariae Radix and Coptidis Rhizoma and prepared coprecipitate of crude baicalin-berberine. To increase the stability and bioavailability of coprecipitate of crude baicalin-berberine(CBB), which is slightly soluble drug, its inclusion complex was prepared and studied in this experiment. Inclusion complex of CBB with ${\beta}-cyclodextrin(CBB-{\beta}-CD)$ was prepared by freeze drying method and its characteristics were ascertained by means of solubility test, differential thermal analysis(DTA) and scanning electron microscope(SEM). The type of $CBB-{\beta}-CD$ is classified as $A_L-type$ on phase solubility diagram, and the stoichiometric ratio of CBB(baicalin in CBB) : ${\beta}-CD$ complex is 1:1 and formation constant is 151 $M^-1$. The solubility, dissolution, in situ absorption and serum concentration of $CBB-{\beta}-CD$ were significantly increased when compared to CBB. Therefore enhanced bioavailability of CBB by inclusion complexation with ${\beta}-cyclodextrin$ might be useful for dosage form design of active ingredients of two herbal medicine.
Precipitation was formed during the preparation of decoction from a mixure of Scutellariae Radix and Coptidis Rhizoma or Phellodendri Cortex according to the prescription of Hwang-ryean-hae-dog-tang. Baicalin and berberine, the active ingredients of the two herbal medicine were identified in coprecipitated product. Pills were prepared using the coprecipitated product and various binders. The dissolution rate of baicalin and berberine from pills was increased in at pH1.2 when acacia or tragacanth was used. The absorption rate of baicalin from the coprecipitated product was faster than that from Scutellaria extract, but the absorption of berberine from CPP was slower in stomach, duodenum and jejunum of rats compared with Coptis extract. The time required for the maximum serum concentration (Cmax) of baicalin and berberine from CPP in mice were 150 and 200 min after oral administration, respectively. The maximum serum concentration of baicalin from CPP in mice was higher than Scutellaria extract, but the concentration of berberine was lower compared with Coptis extract. The minimum inhibitory concentration of CPP was below $50\;{\mu}g/ml$ against gram positive bacteria, and was higher than that against gram negative bacteria. The antibacterial activity of CPP was lower than that of herberine, but was more potent than Scutellaria extract. It was found that the inhibition rates of growth by CPP against S. epidermidis, K. pneumoniae, B. cereus and S.aureus were 60.0, 51.1, 45.4 and 39.9%, respectively.
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