• Title/Summary/Keyword: Thermodynamic

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Determination of Total CO2 and Total Alkalinity of Seawater Based on Thermodynamic Carbonate Chemistry (해수중의 총이산화탄소와 총알칼리도 분석을 위한 탄산염 화학 이론 및 측정방법)

  • Mo, Ahra;Son, Juwon;Park, Yongchul
    • Journal of the Korean Society for Marine Environment & Energy
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    • v.18 no.1
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    • pp.1-8
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    • 2015
  • To evaluate accuracy and precision of determination of total alkalinity ($Alk_T$) and carbon dioxide ($TCO_2$) derived from present study, experiment was applied with $CO_2$ CRM (Batch 132, Scripps Institution of Oceanography; $Alk_T=2229.24{\pm}0.39{\mu}mol/kg$, $TCO_2=2032.65{\pm}0.45{\mu}mol/kg$). As the result, average concentration of $Alk_T$ and $TCO_2$ was $2354.09{\mu}mol/kg$ (~5.6% difference with $CO_2$ CRM) and $2089.60{\mu}mol/kg$ (~2.3% difference with $CO_2$ CRM), respectively. For previous method (Gran Titration) by addition $NaHCO_3$ to deionized water($Alk_T$ $2023.33{\mu}mol/kg$), average concentration was $2193.39{\mu}mol/kg$ (sd=57.15, n=7). Whereas, average concentration was $2017.02{\mu}mol/kg$ (sd=10.98, n=7) for the present study. Recovery yield experiments of total alkalinity in deionized water and seawater were implemented by addition of $NaHCO_3$. The recovery yield of deionized water in the range 0 to $4952.39{\mu}mol/kg$ was 100.8% ($R^2$=0.999), and seawater in the range 0 to $2041.32{\mu}mol/kg$ was 102.3% ($R^2$=0.999). Comparison of $pCO_2$ sensor (PSI $CO_2-Pro^{TM}$) with present method showed very meaningful correlation coefficient ($R^2$=0.977) in the range of 427 to $705{\mu}atm$ and 9.16 to $15.24{\mu}mol/kg$ throught elapsed time for two weeks. Field experiment of diurnal variation of total carbon dioxide was accomplished at Sachon harbor in the coastal waters of East Sea of Korea. Concentration of $Alk_T$ and $TCO_2$ was increased during night, and decreased during daylight hours. The results showed mirror type between $TCO_2$ and dissolved oxygen, which was attributable to photosynthesis and respiration of phytoplankton. Also, open ocean field study was performed to obtain vertical profile of $Alk_T$ and $TCO_2$ in C-C zone (Clarion-Clipperton Fracture Zone), Northeastern Pacific. Average concentrations of $Alk_T$ in the surface mixed layer (0~60 m) and deeper layer below 200 m were $2422.38{\mu}mol/kg$ (sd=78.73, n=20) and $2465.87{\mu}mol/kg$ (sd=57.68, n=103), respectively. And average concentrations of $TCO_2$ were $2134.47{\mu}mol/kg$ (sd=65.4, n=20) and $2431.87{\mu}mol/kg$ (sd=65.02, n=103) in the same depth ranges such as $Alk_T$. Vertical distributions of $Alk_T$ and $TCO_2$ concentrations tended to increase with depth, and analyzed concentrations showed slightly higher than those of previous studies in this area.

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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