• Title/Summary/Keyword: PHREEQC

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Hydrochemistry of an alluvial aquifer in the Cheonan area: role of the pyrite oxidation on denitrification

  • Kim, Kyoung-Ho;Yun, Seong-Taek;Chae, Gi-Tak;Heo, Chul-Ho;Kim, Hyoung-Soo;Rhee, Chul-Woo;Kim, Kangjoo
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2002.09a
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    • pp.287-290
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    • 2002
  • To examine the denitrification process in an alluvial aquifer in the Cheonan site, hydrological and hydrogeochemical studies were carried out. Elevated levels of NO$_3$ (maximum 77.6 mg/L) were observed in shallow groundwaters of the area, as a result of poultry and agricultural activity. However, the nitrate concentrations were found to be consistently attenuated down to very low levels (<1.0 mg/L). The abrupt removal of nitrate coincided with the pattern of redox change and indicated that denitrification is the most plausible process. The hydrochemistry and mass balance approach using geochemical modeling (phreeqc 2.0) and redox chemistry indicated that chemo-autotrophic denitrification via pyrite oxidation is the key Process to control the nitrate attenuation in the study area.

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Marble wastes as amendments to stabilize heavy metals in Zn-Electroplating sludge

  • Riahi, Khalifa;Chaabane, Safa;Thayer, Bechir Ben
    • Advances in environmental research
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    • v.6 no.1
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    • pp.15-23
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    • 2017
  • Powdered marble wastes (PMW) generated by Utique marble cutting industries (North of Tunisia) with abundant amounts were used in this study as low-cost materials to investigate the stabilization of heavy metals (Pb, Zn, Fe) in sludge generated from a local Zn-Electroplating factory. Powdered marble wastes were evaluated by means of chemical fractions of heavy metals in sludge and concentrations of heavy metals in leachate from columns to determine their ability to stabilize heavy metals in contaminated sludge. Results indicated that chemical fractions of heavy metals in sludge were affected by application of the PMW mineral materials and pH, however, the effects varied with heavy metals. Application of the powdered marble wastes mineral materials reduced exchangeable metals in the sequence of Pb (60.5%)>Fe (40.5%)>Zn (30.1%). X-ray diffraction and hydro-geochemical transport code PHREEQC analysis were successfully carried out to get a better understanding of the mechanisms of reactive mineral phases involved in reduced exchangeable heavy metals in sludge after PMW material amendments. Therefore, metal immobilization using powdered marble wastes materials is an effective stabilization technique for industrial metallic hydroxide sludge.

Sorption of Se(-II) on illite, MX-80 bentonite, shale, and limestone in Na-Ca-Cl solutions

  • Walker, Andrew;Racette, Joshua;Saito, Takumi;Yang, Tammy (Tianxiao);Nagasaki, Shinya
    • Nuclear Engineering and Technology
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    • v.54 no.5
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    • pp.1616-1622
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    • 2022
  • Selenium has been identified as an element of interest for the safety assessment of a deep geological repository (DGR) for used nuclear fuel. In Canada, groundwaters at DGR depths in sedimentary rocks have been observed to have a high ionic strength. This paper examines the sorption behavior of Se(-II) onto illite, MX-80 bentonite, Queenston shale, and argillaceous limestone in Na-Ca-Cl solutions of varying ionic strength (0.1-6 mol/kgw (m)) and across a pH range of 4-9. Little ionic strength dependence for Se(-II) sorption onto all solids was observed except that sorption at high ionic strength (6 m) was generally slightly lower than sorption at low ionic strength (0.1 m). Illite and MX-80 exhibited the expected results for anion sorption, while shale and limestone exhibited more constant sorption across the pH range tested. A non-electrostatic surface complexation model successfully predicted sorption of Se(-II) onto illite and MX-80 using the formation of an inner-sphere surface complex and an outer-sphere surface complex. Optimized values for the formation reactions of these surface species were proposed.

A geochemical study on the saline waters circulating in an ash disposal pond of Seocheon Power Plant. Korea

  • Kim, Kang-Joo;Park, Seong-Min;Kim, Jin-San;Natarajan Rajmohan;Hwang, Gab-Soo;Yun, Seong-Taek;Kim, Hyun-Jung;Kim, Suk-Hwi
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2004.09a
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    • pp.338-341
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    • 2004
  • This study was carried out to understand the geochemistry of saline water circulating in an ash disposal pond of Seocheon power plant, Korea. For this study, ash pond waters, slurry water and seawater samples were collected and analyzed for major ions and trace elements. Results show that ash pond waters and slurry water are alkaline in nature due to high calcium content, and have high concentration of Ca, B, Li, As, Ba, Al, Si and Mn over seawater, suggest that these elements leached from fly ash even at high alkaline condition and ionic strength. Slurry water has high concentration of B, Ba, Li, Mn, Si and Sr compare to ash pond waters, expresses that these elements seem to be easily reached at initial stage fly ash-water interaction, and also might be associated with the surface of the fly ash particles. Additionally, PHREEQC program predicted several secondary solid phases, which are also influenced in the leaching of elements in to the saline water.

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EFFECT OF CARBONATE ON THE SOLUBILITY OF NEPTUNIUM IN NATURAL GRANITIC GROUNDWATER

  • Kim, B.Y.;Oh, J.Y.;Baik, M.H.;Yun, J.I.
    • Nuclear Engineering and Technology
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    • v.42 no.5
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    • pp.552-561
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    • 2010
  • This study investigates the solubility of neptunium (Np) in the deep natural groundwater of the Korea Atomic Energy Research Institute Underground Research Tunnel (KURT). According to a Pourbaix diagram (pH-$E_h$ diagram) that was calculated using the geochemical modeling program PHREEQC 2.0, the redox potential and the carbonate ion concentration both control the solubility of neptunium. The carbonate effect becomes pronounced when the total carbonate concentration is higher than $1.5\;{\times}\;10^{-2}$ M at $E_h$ = -200 mV and the pH value is 10. Given the assumption that the solubility-limiting stable solid phase is $Np(OH)_4(am)$ under the reducing condition relevant to KURT, the soluble neptunium concentrations were in the range of $1\;{\times}\;10^{-9}$ M to $3\;{\times}\;10^{-9}$ M under natural groundwater conditions. However, the solubility of neptunium, which was calculated with the formation constants of neptunium complexes selected in an OECD-NEA TDB review, strongly deviates from the value measured in natural groundwater. Thus, it is highly recommended that a prediction of neptunium solubility is based on the formation constants of ternary Np(IV) hydroxo-carbonato complexes, even though the presence of those complexes is deficient in terms of the characterization of neptunium species. Based on a comparison of the measurements and calculations of geochemical modeling, the formation constants for the "upper limit" of the Np(IV) hydroxo-carbonato complexes, namely $Np(OH)_y(CO_3)_z^{4-y-2z}$, were appraised as follows: log $K^{\circ}_{122}\;=\;-3.0{\pm}0.5$ for $Np(OH)_2(CO_3)_2^{2-}$, log $K^{\circ}_{131}\;=\;-5.0{\pm}0.5$ for $Np(OH)_3(CO_3)^-$, and log $K^{\circ}_{141}\;=\;-6.0{\pm}0.5$ for $Np(OH)_4(CO_3)^{2-}$.

REVIEW AND COMPILATION OF DATA ON RADIONUCLIDE MIGRATION AND RETARDATION FOR THE PERFORMANCE ASSESSMENT OF A HLW REPOSITORY IN KOREA

  • Baik, Min-Hoon;Lee, Seung-Yeop;Lee, Jae-Kwang;Kim, Seung-Soo;Park, Chung-Kyun;Choi, Jong-Won
    • Nuclear Engineering and Technology
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    • v.40 no.7
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    • pp.593-606
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    • 2008
  • In this study, data on radionuclide migration and retardation processes in the engineered and natural barriers of High-Level Radioactive Waste (HLW) repository have been reviewed and compiled for use in the performance assessment of a HLW disposal system in Korea. The status of the database on radionuclide migration and retardation that is being developed in Korea is investigated and summarized in this study. The solubilities of major actinides such as D, Th, Am, Np, and Pu both in Korean bentonite porewater and in deep Korean groundwater are calculated by using the geochemical code PHREEQC (Ver. 2.0) based on the KAERI-TDB(Korea Atomic Energy Research Institute-Thermochemical Database), which is under development. Databases for the diffusion coefficients ($D^b_e$ values) and distribution coefficients ($K^b_d$ values) of some radionuclides in the compacted Korean Ca-bentonite are developed based upon domestic experimental results. Databases for the rock matrix diffusion coefficients ($D^r_e$ values) and distribution coefficients ($K^r_d$ values) of some radionuclides for Korean granite rock and deep groundwater are also developed based upon domestic experimental results. Finally, data related to colloids such as the characteristics of natural groundwater colloids and the pseudo-colloid formation constants ($K_{pc}$ values) are provided for the consideration of colloid effects in the performance assessment.

COMPARISON BETWEEN EXPERIMENTALLY MEASURED AND THERMODYNAMICALLY CALCULATED SOLUBILITIES OF UO2 AND THO2 IN KURT GROUND WATER

  • Kim, Seung-Soo;Baik, Min-Hoon;Kang, Kwang-Cheol;Choi, Jong-Won
    • Nuclear Engineering and Technology
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    • v.41 no.6
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    • pp.867-874
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    • 2009
  • Solubility of a radionuclide is important for defining the release source term of a radioactive waste in the safety and performance assessments of a radioactive waste repository. When the pH and redox potential of the KURT groundwater were changed by an electrical method, the concentrations of uranium and thorium released from $UO_2$(cr) and $ThO_2$(cr) at alkali pH(8.1 ${\sim}$ 11.4) and reducing potential (Eh < -0.2 V) conditions were less than $10^{-7}mole/L$. Unexpectedly, the concentration of tetravalent thorium is slightly higher than that of uranium at pH = 8.1 and Eh= -0.2 V conditions, and this difference may be due to the formation of hydroxide-carbonate complex ions. When $UO_2$(s) and $UO_2$(am, hyd.), and $ThO_2$(s) and $Th(OH)_4(am)$ were assumed as solubility limiting solid phases, the concentrations of uranium and thorium in the KURT groundwater calculated by the PHREEQC code were comparable to the experimental results. The dominating aqueous species of uranium and thorium were presumed as $UO_2(CO_3)_3^{4-}$ and $Th(OH)_3CO_3^-$ at pH = 8.1 ${\sim}$ 9.8, and $UO_2(OH)_3^-$ and $Th(OH)_4(aq)$ at pH = 11.4.

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
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    • v.7 no.3
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    • pp.103-115
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    • 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.

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Arsenic Distribution and Solubility in Groundwater of Okcheon Area (옥천군 북부 지역 지하수의 비소 분포와 비소 광물의 용해도 특성)

  • Chon, Chul-Min;Kim, Kue-Young;Koh, Dong-Chon;Choi, Mi-Jung
    • Journal of the Mineralogical Society of Korea
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    • v.22 no.4
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    • pp.331-342
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    • 2009
  • Groundwater samples were collected from the bedrock aquifers related with Okcheon metasedimentary rocks. Arsenic (As) concentrations in the samples varied between 0.0051 and 0.887 mg/L, with an average of 0.0248. Cations and anions of groundwaters had no relationship with As contents as well as with spatial distribution of geology in the area. Pyrite, chalcopyrite and arsenopyrite in the core samples of the monitoring wells were identified in thin section, X-ray diffraction (XRD) and electron probe microscope analysis (EPMA). It was suggested that these minerals are responsible for the As in groundwater. The groundwater showed saturations with respect to calcite $(CaCO_3)$, dolomite (CaMg$(CO_3)_2$) and Magnesite $(MgCO_3)$. $HAsO_4{^{2-}}$ activities in the groundwater samples were close to $Ca_3(AsO_4)_2(c)$ and $Mn_3(AsO_4)_2(c)$ solubility isotherms, indicating that the maximum As contents in groundwater are secondly controlled by the precipitation and dissolution of carbonate minerals due to alkaline and oxic nature of the groundwater (pe+pH>10).

A Study on groundwater and pollutant recharge in urban area: use of hydrochemical data

  • Lee, Ju-Hee;Kwon, Jang-Soon;Yun, Seong-Taek;Chae, Gi-Tak;Park, Seong-Sook
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2004.09a
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    • pp.119-120
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    • 2004
  • Urban groundwater has a unique hydrologic system because of the complex surface and subsurface infrastructures such as deep foundation of many high buildings, subway systems, and sewers and public water supply systems. It generally has been considered that increased surface impermeability reduces the amount of groundwater recharge. On the other hand, leaks from sewers and public water supply systems may generate the large amounts of recharges. All of these urban facilities also may change the groundwater quality by the recharge of a myriad of contaminants. This study was performed to determine the factors controlling the recharge of deep groundwater in an urban area, based on the hydrogeochemical characteristics. The term ‘contamination’ in this study means any kind of inflow of shallow groundwater regardless of clean or contaminated. For this study, urban groundwater samples were collected from a total of 310 preexisting wells with the depth over 100 m. Random sampling method was used to select the wells for this study. Major cations together with Si, Al, Fe, Pb, Hg and Mn were analyzed by ICP-AES, and Cl, N $O_3$, N $H_4$, F, Br, S $O_4$and P $O_4$ were analyzed by IC. There are two groups of groundwater, based on hydrochemical characteristics. The first group is distributed broadly from Ca-HC $O_3$ type to Ca-C1+N $O_3$ type; the other group is the Na+K-HC $O_3$ type. The latter group is considered to represent the baseline quality of deep groundwater in the study area. Using the major ions data for the Na+K-HC $O_3$ type water, we evaluated the extent of groundwater contamination, assuming that if subtract the baseline composition from acquired data for a specific water, the remaining concentrations may indicate the degree of contamination. The remainder of each solute for each sample was simply averaged. The results showed that both Ca and HC $O_3$ represent the typical solutes which are quite enriched in urban groundwater. In particular, the P$CO_2$ values calculated using PHREEQC (version 2.8) showed a correlation with the concentrations of maior inorganic components (Na, Mg, Ca, N $O_3$, S $O_4$, etc.). The p$CO_2$ values for the first group waters widely ranged between about 10$^{-3.0}$ atm to 10$^{-1.0}$ atm and differed from those of the background water samples belonging to the Na+K-HC $O_3$ type (<10$^{-3.5}$ atm). Considering that the p$CO_2$ of soil water (near 10$^{-1.5}$ atm), this indicates that inflow of shallow water is very significant in deep groundwaters in the study area. Furthermore, the P$CO_2$ values can be used as an effective parameter to estimate the relative recharge of shallow water and thus the contamination susceptibility. The results of our present study suggest that down to considerable depth, urban groundwater in crystalline aquifer may be considerably affected by the recharge of shallow water (and pollutants) from an adjacent area. We also suggest that for such evaluation, careful examination of systematically collected hydrochemical data is requisite as an effective tool, in addition to hydrologic and hydrogeologic interpretation.ion.ion.

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