• Title/Summary/Keyword: Oxidation kinetics

Search Result 271, Processing Time 0.026 seconds

Mechanisms of Immobilization and Leaching Characteristics of Arsenic in the Waste Rocks and Tailings of the Abandoned Mine Areas (폐광산 지역 폐광석 및 광미에서 비소의 고정 메커니즘과 용출특성)

  • Kang Min-Mu;Lee Pyeong-Koo
    • Economic and Environmental Geology
    • /
    • v.38 no.5 s.174
    • /
    • pp.499-512
    • /
    • 2005
  • EPMA determined that Fe(Mn)-(oxy)hydroxides and well-crystallized Fe-(oxy)hydroxides and could contain a small amount of As $(0.3-11.0\;wt.\%\;and\;2.1-7.4\;wt.\%\;respectively)$. Amorphous crystalline Fe-(oxy) hydroxide assemblages were identified as the richest in As with $28-36\;wt.\%$. On the ternary $As_2O_5-SO_3-Fe_2O_3$ diagram, these materials were interpreted here as 'scorodite-like'. Dissolved As was attenuated by the adsorption on Fe-(oxy) hydroxides and Fe(Mn)-(oxy) hydroxides and/or the formation of an amorphous Fe-As phase (maybe scorodite: $FeAsO_4\cdot2H_2O$). Leaching tests were performed in order to find out leaching characteristics of As and Fe under acidic conditions. At the initial pHs 3 and 5, As contents dissolved from tailings of the cheongyang mine significantly increased after 7 days due to the oxidation of As-bearing secondary minerals (up to ca. $2.4\%$ of total), while As of Seobo mine-tailing samples was rarely released (ca. $0.0-0.1\%$ of total). Dissolution experiments at an initial pH 1 liberated a higher amount of As (ca. $1.1-4.2\%$ of total for Seobo tailings, $1.5-14.4\%$ of total for Cheongyang tailings). In addition, good correlation between As and Fe in leached solutions with tailings was observed. The kinetic problems could be the important factor which leads to increasing concentrations of As in the runoff water. Release of As from Cheongyang tailings can potentially pose adverse impact to surface and groundwater qualities in the surrounding environment, while precipitation of secondary minerals and the adsorption of As are efficient mechanisms for decreasing the mobilities of As in the surface environment of Seobo mine area.

Kinetics and mechanism of chromate reduction by biotite and pyrite (흑운모 및 황철석에 의한 6가 크롬의 환원 반응속도와 반응기작)

  • 전철민;김재곤;문희수
    • Economic and Environmental Geology
    • /
    • v.36 no.1
    • /
    • pp.39-48
    • /
    • 2003
  • The removal of chromate from aqueous solution using finely ground pyrite and biotite was investigated by batch experiments and the kinetics and the mechanism of chromate reduction were discussed. The chromate reduction by pyrite was about hundred times faster than that by biotite and was also faster at pH 3 than at pH 4. When pyrite was used, more than 90% of initial chromate was reduced within four hours at pH 4 and within 40 min. at pH 3. However, more than 400 hours was taken for the reduction of 90% of initial chromate by biotite. The results indicate that the rate of chromate reduction was strongly depending on the amount of Fe(II) in the minerals and on the dissolution rate of Fe(II) from the minerals. The reduction of chromate at pH 4 resulted in the precipitation of (Cr, Fe)(OH))$_3$$_{ (s)}$, which is believed to have limited the concentrations of dissolved Cr(III) and Fe(III) to less than expected values. When biotite was used, amounts of decreased Fe(II) and reduced Cr(Ⅵ) did not show stoichiometric relationship, which implying there was not only chromate reduction by ferrous ions in the acidic solution but also heterogeneous reduction of ferric ions by the structural ferrous iron in biotite. However, the results from a series of the experiments using Pyrite showed that concentrations of the decreased Fe(II) and the reduced Cr(Ⅵ) were close to the stoichiometric ratio of 3:1. It was because the oxidation of pyrite rapidly created ferrous ions even in oxygenated solutions and the chromate reduction by the ferrous ions was significantly faster than ferrous ion oxygenation.

Effects of Rice Straw and Gypsum on the Changes of Urease, Nitrate Reductase and Nitrite Reductase Activities in Saline Paddy Soil (간척답토양(干拓沓土壤)에 볏짚 및 석고시용(石膏施用)이 뇨효소(尿酵素), 초산환원효소(硝酸還元酵素) 및 아초산환원효소(亞硝酸還元酵素)의 활성(活性)에 미치는 영향(影響))

  • Lee, Sang Kyu;Kim, Young Sig;Hwang, Seon Woong;Park, Jun Kyu;Chang, Young Sun
    • Korean Journal of Soil Science and Fertilizer
    • /
    • v.18 no.1
    • /
    • pp.105-110
    • /
    • 1985
  • A incubation study was conducted to find out the effects of rice straw and gypsum as soil ameriolite on urease, nitrate and nitrite reductase activities in newly reclaimed saline sandy soil. The results obtained were summarized as follows: 1. Very low urease activities were observed in saline soil if contrast to high productive paddy soil. Urease activities were lower at 5 days than that of 25 and 50 days after incubation. Remarkably high urease activities were obtained by the application of rice straw and gypsum. 2. Comparing with NPK treatment, application of rice straw and gypsum were enhanced the activities of nitrate and nitraite reductase. 3. Positive correlation (r=0.5501 p=0.05) was obtained between urease activities and ammonium nitrogen concentration in soil. 4. Cyclic oxidation and reduction of nitrate and nitrite in soil were obtained in terms of first order microbial kinetics reaction in case of application of rice straw and gypsum, respectively. 5. Positive correlation (r=0.6296 p=0.05) was obtained between the activitie of nitrite reductase and nitrate reductase in soil.

  • PDF

Reductive stripping of Np using a n-butyraldehyde from a loaded TBP phase containing Np (Np 함유 TBP 유기상으로부터 NBA에 의한 Np의 환원 역추출)

  • Lee, Eil-Hee;Lim, Jae-Kwan;Chung, Dong-Yong;Yang, Han-Beom;Kim, Kwang-Wook
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
    • /
    • v.6 no.3
    • /
    • pp.163-170
    • /
    • 2008
  • The reductive stripping of Np using a n-butyraldehyde (NBA) from loaded organic solution containing Np, which was oxidative-extracted in a system of a 30 % TBP/NDD-2M $HNO_3$ and O/A=2 containing 0.005 M $K_2Cr_2O_7$ as an oxidant of Np, was studied. The stripping yields of Np was increased with an increasing the NBA concentration, with a decreasing the nitric acid concentration of stripping solution and with a decreasing the reaction temperature. The apparent reductive stripping rate equation was shown by the following equation : $-d[Np]_{Org.}/dt$ = 1,524 exp(-2,906/T) $[NBA]^{0.91}\;[H^+]^{-0.92}[Np]_{Org.}$. At 1.04 M NBA and 2 M $NHO_3$, the stripping yield of Np and U was 70.1 %, and 7.1 %, respectively, and the separation factor of U over Np ($=D_U/D_{Mp}$) was about 30.4. Therefore, it was found that U and Np co-extracted in a system of TBP-$HNO_3$ could be effectively mutual-separated by the NBA.

  • PDF

The Effect of Fumed Silica on Nitrate Reduction by Zero-valent Iron (흄드 실리카가 영가철에 의한 질산성질소 환원에 미치는 영향)

  • Cho, Dong-Wan;Jeon, Byong-Hun;Kim, Yong-Je;Song, Ho-Cheol
    • Journal of Korean Society of Environmental Engineers
    • /
    • v.32 no.6
    • /
    • pp.599-608
    • /
    • 2010
  • The effect of silica(fumed) on nitrate reduction by zero-valent iron(ZVI) was studied using batch experiment. The reduction of nitrate was tested in three different aqueous media including de-ionized water, artificial groundwater and real groundwater contaminated by nitrate. Kinetics of nitrate reduction in groundwater were faster than those in de-ionized water, and first-order rate constant($k_{obs}$) of ZVI/silica(fumed) process was about 2.5 time greater than that of ZVI process in groundwater. Amendment of Silica(fumed) also decreased ammonium presumably through adsorption on silica surface. The pHs in all processes increased due to oxidation of ZVI, but the increase was lower in groundwater due to buffering capacity of groundwater. The result also showed amount of reduced nitrate increased as initial nitrate concentration increased in groundwater. Separate adsorption isotherm experiments indicated that fumed silica itself had some degree of adsorption capacity for ammonium. The overall results indicated that silica(fumed) might be a promising material for enhancing nitrate reduction by ZVI.

Micelles in Physical Chemistry Laboratory. Surfactant Catalyzed Oxidation of Glycine by Acidic Permanganate

  • Pare, Brijesh;Kaur, Parwinder;Bhagwat, V.W.;Fogliani, Charles
    • Journal of the Korean Chemical Society
    • /
    • v.48 no.2
    • /
    • pp.195-202
    • /
    • 2004
  • Micellar catalysis is an essential part of theoretical and experimental curricular. The sodium dodecylsulfate (SDS) catalyzed reaction between glycine and potassium permanganate in acidic medium is an ideal kinetic experiment for the secondary and undergraduate physical chemistry laboratory, to show the effect of micellar catalysis on rate of the reaction. The reaction is conducted both with and without SDS to observe the rate enhancement in the presence of surfactant. To show surfactant catalysis a plot between k and [SDS] is plotted. As surfactant catalysis is observed even before the critical micelle concentration of SDS, this pre-micellar catalysis can be understood in the light of positive co-operativity. The value of positive cooperative index (n) has been found to be 2.37. Further, dependence of the reaction rate on substrate and oxidant concentrations is also discussed. The reaction follows pseudo-first-order kinetics. The overall reaction is second order, with first-order dependence on both glycine and permanganate concentrations. The theory of surfactant catalysis is also discussed. With the conditions specified in the experiment, total reaction times are in 3~4 hours lab session, thus allowing several data sets to be acquired in a single laboratory period. Preparation of solutions and procedure is also given in detail.

Thermal Decomposition of A New Insecticide KH-502 [O, O-Diethyl O-(1-phenyl -3-trifluoromethy-5-pyrazoyl) thiophosphoric acid ester] (신규(新規) 살충제(殺蟲劑)인 O, O, O-Diethyl-O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl) thiophosphoric acid ester의 열(熱)에 의한 분해성(分解性))

  • Cho, Boo-Yeon;Han, Dae-Sung
    • Korean Journal of Environmental Agriculture
    • /
    • v.11 no.3
    • /
    • pp.225-234
    • /
    • 1992
  • Thermal decomposition was conducted to investigate the influence of the various factors on stability of a new insecticide, [O, O-Diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl) thiophosphoric acid ester : KH-502], in view of those informations applicable for industrial exploitation. In the thermal decomposition experiment, KH-502 was, after mixing with Fe, Cu and adjustment of moisture and pH conditions, subjected to three temperatures, 25, 50, and $100^{\circ}C$. Results for stability, and degradation pattern of KH-502 from the above experiment can be summarized as follows: 1. Main products of the thermal decomposition when this was conducted in the closed system were identified as following five compounds:O, O, O-Triethylthiophosphoric acid(TEPA), 1-Phenyl-3-trifluoromethyl-5-ethoxypyrazole(PTMEP), 1-Phenyl-2-ethyl-3-trifluoromethyl-5-hydroxypyrazole(PETMHP), O, O-Diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phosphoric acid ester(KH-502 oxo form), O, S-Diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phospho rothiolate(S-ethyl KH-502). However, compounds such as oxo form and S-ethyl KH-502 were not identified when the thermal decomposition was proceeded in the open system. 2. KH-502 was stable at 25 and 50$^{\circ}C$, but it was decomposed at 100$^{\circ}C$ following the first-order kinetics at the early stages of decomposition. 3. Rate constants for the thermal decomposition of KH-502 at 100$^{\circ}C$ were in the orders of Cu powder addition 0.344>Cu plate addition 0.21>moisture addition 0.05>closed system=open system=iron addition=pH 5.5 adjustment 0.04>pH 8.5 adjustment 0.027 day$^{-1}$, representing KH-502 was decomposed fast at Cu powder treatment and slow at pH 8.5 adjustment. 4. Half-life for the thermal decomposition of KH-502 at 100$^{\circ}C$ was in the orders of Cu powder addition 2.02

  • PDF

Improved Performance of Direct Carbon Fuel Cell by Catalytic Gasification of Ash-free Coal (무회분탄 연료의 촉매 가스화에 의한 직접탄소연료전지의 성능 향상)

  • Jin, Sunmi;Yoo, Jiho;Rhee, Young Woo;Choi, Hokyung;Lim, Jeonghwan;Lee, Sihyun
    • Clean Technology
    • /
    • v.18 no.4
    • /
    • pp.426-431
    • /
    • 2012
  • Carbon-rich coal can be utilized as a fuel for direct carbon fuel cell (DCFC). However, left-behind ash after the electrochemical oxidation may hinder the electrochemical reactions. In this study, we produced ash-free coal (AFC) by thermal extraction and then tested it as a fuel for DCFC. DCFC was built based on solid oxide electrolyte and the electrochemical performance of AFC mixed with $K_2CO_3$ was compared with AFC only. Significantly enhanced power density was found by catalytic steam gasification of AFC. However, an increase of the power density by catalytic pyrolysis was negligible. This result indicated that a catalyst activated the steam gasification reactions, producing much more $H_2$ and thus increasing the power density, compared to AFC only. Results of a quantitative analysis showed much improved kinetics in AFC with $K_2CO_3$ in agreement with DCFC results. A secondary phase of potassium on yttria-stabilized zirconia (YSZ) surface was observed after the cell operation. This probably caused poor long-term behavior of AFC with $K_2CO_3$. A thin YSZ (30 ${\mu}m$ thick) was found to be higher in the power density than 0.9 mm of YSZ.

Field Studios of In-situ Aerobic Cometabolism of Chlorinated Aliphatic Hydrocarbons

  • Semprini, Lewts
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
    • /
    • 2004.04a
    • /
    • pp.3-4
    • /
    • 2004
  • Results will be presented from two field studies that evaluated the in-situ treatment of chlorinated aliphatic hydrocarbons (CAHs) using aerobic cometabolism. In the first study, a cometabolic air sparging (CAS) demonstration was conducted at McClellan Air Force Base (AFB), California, to treat chlorinated aliphatic hydrocarbons (CAHs) in groundwater using propane as the cometabolic substrate. A propane-biostimulated zone was sparged with a propane/air mixture and a control zone was sparged with air alone. Propane-utilizers were effectively stimulated in the saturated zone with repeated intermediate sparging of propane and air. Propane delivery, however, was not uniform, with propane mainly observed in down-gradient observation wells. Trichloroethene (TCE), cis-1, 2-dichloroethene (c-DCE), and dissolved oxygen (DO) concentration levels decreased in proportion with propane usage, with c-DCE decreasing more rapidly than TCE. The more rapid removal of c-DCE indicated biotransformation and not just physical removal by stripping. Propane utilization rates and rates of CAH removal slowed after three to four months of repeated propane additions, which coincided with tile depletion of nitrogen (as nitrate). Ammonia was then added to the propane/air mixture as a nitrogen source. After a six-month period between propane additions, rapid propane-utilization was observed. Nitrate was present due to groundwater flow into the treatment zone and/or by the oxidation of tile previously injected ammonia. In the propane-stimulated zone, c-DCE concentrations decreased below tile detection limit (1 $\mu$g/L), and TCE concentrations ranged from less than 5 $\mu$g/L to 30 $\mu$g/L, representing removals of 90 to 97%. In the air sparged control zone, TCE was removed at only two monitoring locations nearest the sparge-well, to concentrations of 15 $\mu$g/L and 60 $\mu$g/L. The responses indicate that stripping as well as biological treatment were responsible for the removal of contaminants in the biostimulated zone, with biostimulation enhancing removals to lower contaminant levels. As part of that study bacterial population shifts that occurred in the groundwater during CAS and air sparging control were evaluated by length heterogeneity polymerase chain reaction (LH-PCR) fragment analysis. The results showed that an organism(5) that had a fragment size of 385 base pairs (385 bp) was positively correlated with propane removal rates. The 385 bp fragment consisted of up to 83% of the total fragments in the analysis when propane removal rates peaked. A 16S rRNA clone library made from the bacteria sampled in propane sparged groundwater included clones of a TM7 division bacterium that had a 385bp LH-PCR fragment; no other bacterial species with this fragment size were detected. Both propane removal rates and the 385bp LH-PCR fragment decreased as nitrate levels in the groundwater decreased. In the second study the potential for bioaugmentation of a butane culture was evaluated in a series of field tests conducted at the Moffett Field Air Station in California. A butane-utilizing mixed culture that was effective in transforming 1, 1-dichloroethene (1, 1-DCE), 1, 1, 1-trichloroethane (1, 1, 1-TCA), and 1, 1-dichloroethane (1, 1-DCA) was added to the saturated zone at the test site. This mixture of contaminants was evaluated since they are often present as together as the result of 1, 1, 1-TCA contamination and the abiotic and biotic transformation of 1, 1, 1-TCA to 1, 1-DCE and 1, 1-DCA. Model simulations were performed prior to the initiation of the field study. The simulations were performed with a transport code that included processes for in-situ cometabolism, including microbial growth and decay, substrate and oxygen utilization, and the cometabolism of dual contaminants (1, 1-DCE and 1, 1, 1-TCA). Based on the results of detailed kinetic studies with the culture, cometabolic transformation kinetics were incorporated that butane mixed-inhibition on 1, 1-DCE and 1, 1, 1-TCA transformation, and competitive inhibition of 1, 1-DCE and 1, 1, 1-TCA on butane utilization. A transformation capacity term was also included in the model formation that results in cell loss due to contaminant transformation. Parameters for the model simulations were determined independently in kinetic studies with the butane-utilizing culture and through batch microcosm tests with groundwater and aquifer solids from the field test zone with the butane-utilizing culture added. In microcosm tests, the model simulated well the repetitive utilization of butane and cometabolism of 1.1, 1-TCA and 1, 1-DCE, as well as the transformation of 1, 1-DCE as it was repeatedly transformed at increased aqueous concentrations. Model simulations were then performed under the transport conditions of the field test to explore the effects of the bioaugmentation dose and the response of the system to tile biostimulation with alternating pulses of dissolved butane and oxygen in the presence of 1, 1-DCE (50 $\mu$g/L) and 1, 1, 1-TCA (250 $\mu$g/L). A uniform aquifer bioaugmentation dose of 0.5 mg/L of cells resulted in complete utilization of the butane 2-meters downgradient of the injection well within 200-hrs of bioaugmentation and butane addition. 1, 1-DCE was much more rapidly transformed than 1, 1, 1-TCA, and efficient 1, 1, 1-TCA removal occurred only after 1, 1-DCE and butane were decreased in concentration. The simulations demonstrated the strong inhibition of both 1, 1-DCE and butane on 1, 1, 1-TCA transformation, and the more rapid 1, 1-DCE transformation kinetics. Results of tile field demonstration indicated that bioaugmentation was successfully implemented; however it was difficult to maintain effective treatment for long periods of time (50 days or more). The demonstration showed that the bioaugmented experimental leg effectively transformed 1, 1-DCE and 1, 1-DCA, and was somewhat effective in transforming 1, 1, 1-TCA. The indigenous experimental leg treated in the same way as the bioaugmented leg was much less effective in treating the contaminant mixture. The best operating performance was achieved in the bioaugmented leg with about over 90%, 80%, 60 % removal for 1, 1-DCE, 1, 1-DCA, and 1, 1, 1-TCA, respectively. Molecular methods were used to track and enumerate the bioaugmented culture in the test zone. Real Time PCR analysis was used to on enumerate the bioaugmented culture. The results show higher numbers of the bioaugmented microorganisms were present in the treatment zone groundwater when the contaminants were being effective transformed. A decrease in these numbers was associated with a reduction in treatment performance. The results of the field tests indicated that although bioaugmentation can be successfully implemented, competition for the growth substrate (butane) by the indigenous microorganisms likely lead to the decrease in long-term performance.

  • PDF

Geochemical Equilibria and Kinetics of the Formation of Brown-Colored Suspended/Precipitated Matter in Groundwater: Suggestion to Proper Pumping and Turbidity Treatment Methods (지하수내 갈색 부유/침전 물질의 생성 반응에 관한 평형 및 반응속도론적 연구: 적정 양수 기법 및 탁도 제거 방안에 대한 제안)

  • 채기탁;윤성택;염승준;김남진;민중혁
    • Journal of the Korean Society of Groundwater Environment
    • /
    • v.7 no.3
    • /
    • pp.103-115
    • /
    • 2000
  • The formation of brown-colored precipitates is one of the serious problems frequently encountered in the development and supply of groundwater in Korea, because by it the water exceeds the drinking water standard in terms of color. taste. turbidity and dissolved iron concentration and of often results in scaling problem within the water supplying system. In groundwaters from the Pajoo area, brown precipitates are typically formed in a few hours after pumping-out. In this paper we examine the process of the brown precipitates' formation using the equilibrium thermodynamic and kinetic approaches, in order to understand the origin and geochemical pathway of the generation of turbidity in groundwater. The results of this study are used to suggest not only the proper pumping technique to minimize the formation of precipitates but also the optimal design of water treatment methods to improve the water quality. The bed-rock groundwater in the Pajoo area belongs to the Ca-$HCO_3$type that was evolved through water/rock (gneiss) interaction. Based on SEM-EDS and XRD analyses, the precipitates are identified as an amorphous, Fe-bearing oxides or hydroxides. By the use of multi-step filtration with pore sizes of 6, 4, 1, 0.45 and 0.2 $\mu\textrm{m}$, the precipitates mostly fall in the colloidal size (1 to 0.45 $\mu\textrm{m}$) but are concentrated (about 81%) in the range of 1 to 6 $\mu\textrm{m}$in teams of mass (weight) distribution. Large amounts of dissolved iron were possibly originated from dissolution of clinochlore in cataclasite which contains high amounts of Fe (up to 3 wt.%). The calculation of saturation index (using a computer code PHREEQC), as well as the examination of pH-Eh stability relations, also indicate that the final precipitates are Fe-oxy-hydroxide that is formed by the change of water chemistry (mainly, oxidation) due to the exposure to oxygen during the pumping-out of Fe(II)-bearing, reduced groundwater. After pumping-out, the groundwater shows the progressive decreases of pH, DO and alkalinity with elapsed time. However, turbidity increases and then decreases with time. The decrease of dissolved Fe concentration as a function of elapsed time after pumping-out is expressed as a regression equation Fe(II)=10.l exp(-0.0009t). The oxidation reaction due to the influx of free oxygen during the pumping and storage of groundwater results in the formation of brown precipitates, which is dependent on time, $Po_2$and pH. In order to obtain drinkable water quality, therefore, the precipitates should be removed by filtering after the stepwise storage and aeration in tanks with sufficient volume for sufficient time. Particle size distribution data also suggest that step-wise filtration would be cost-effective. To minimize the scaling within wells, the continued (if possible) pumping within the optimum pumping rate is recommended because this technique will be most effective for minimizing the mixing between deep Fe(II)-rich water and shallow $O_2$-rich water. The simultaneous pumping of shallow $O_2$-rich water in different wells is also recommended.

  • PDF