다양한 농도의 복합 중금속으로 오염된 지하수 정화를 위한Calcium polysulfide (CPS)의 최적 주입량 도출 = Optimal Injection Dosage Determination of Calcium polysulfide (CPS) for Remediation of Groundwater Contaminated with Complex Heavy Metals with Various Concentration Ranges

다국어 초록 (Multilingual Abstract)

This study assessed the optimal injection dosage of calcium polysulfide (CPS) for the remediation of groundwatercontaminated with cadmium (Cd) and zinc (Zn) at varying concentrations. CPS, a powerful reducing agent, was applied togroundwater samples from two contaminated sites with high and low heavy metal levels. Increasing CPS dosage resultedin higher pH and lower oxidation-reduction potential (ORP). In the high-concentration sample, a CPS dosage of 0.3% achievedover 99% removal of Cd and Zn, with CPS/heavy metal mass ratios of 2.29 for Cd and 3.13 for Zn. In the low-concentrationsample, CPS dosages between 0.03% and 0.06% also achieved 99% removal but required higher mass ratios (15.88 for Cd and5.33 for Zn). Surface analysis using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy with energydispersiveX-ray spectroscopy (SEM-EDS) confirmed the formation of metal sulfides such as CdS and ZnS. The findingssuggest that lower metal concentrations necessitate higher CPS-to-metal ratios for effective remediation, underscoring theimportance of site-specific optimization of CPS injection for stabilizing heavy metals in groundwater.

참고문헌 (Reference)

1 XPS Database, "XPS Reference Database"

2 "XPS Periodic Table" Thermo Fisher Scientific

3 Simon, P., "X-Ray photoelecrton spectroscopy (XPS): Principles and application for the analysis of photoactive materials" Springer 249-271, 2022

4 "U.S. FRTR"

5 Finney, A. R., "Theoretical and computational approaches to study crystal nucleation from solution" Wiley 2023

6 Akiyama, M., "The Capture of Cadmium by Reactive Polysulfides Attenuates Cadmium-Induced Adaptive Responses and Hepatotoxicity" 30 (30): 2209-2217, 2017

7 Asmare, G., "Tannery wastewater treatment by coagulation-flocculation technique using combination of calcium polysulfide and ferrous sulphate" 9 (9): 79-83, 2021

8 Dupin, J. C., "Systematic XPS studies of metal oxides, hydroxides and peroxides" 2 (2): 1319-1324, 2000

9 Tu, C., "Stabilizing effects on a cadmium polluted coastal wetland soil using calcium polysulphide" 332 : 190-197, 2018

10 Li, Y. Y., "Stability properties of chromium in Cr(VI)-contaminated soil stabilized by calcium polysulfide(CaS5)" 20 (20): 377-383, 2021

11 Soya, K., "Selective sulfidation of copper, zinc and nickel in plating wastewater using calcium sulfide" 44 : 356-362, 2008

12 Lewis, A. E., "Review of Metal Sulfide Precipitation" 104 : 222-234, 2010

13 Prokkola, H., "Removal of metals by sulphide precipitation using Na2S and HS-solution" 4 (4): 51-, 2020

14 Esalah, J. O., "Removal of lead, cadmium and zinc from aqueous solutions by precipitation with sodium Di-(n-Octyl)phosphinate" 78 (78): 945-952, 2000

15 Pohl, A., "Removal of heavy metal ions from water and wastewaters by sulfur-containing precipitation agents" 231 : 503-, 2020

16 Yoon, S., "Removal of cadmium and zinc by calcium polysulfide in acidic groundwater : Injection ratio and precipitation mechanism" 364 : 143219-, 2024

17 Zhang, T., "Reduction and stabilization of Cr(VI)in soil by using calcium polysulfide : Catalysis of natural iron oxides" 190 : 109992-, 2020

18 Teh, C. Y., "Recent advancement of coagulation-flocculation and its application in wastewater treatment" 55 (55): 4363-4389, 2016

19 Cheng, S., "Preparation of calcium polysulfide to remediate groundwater contaminated by hexavalent chromium" 518-524, 2018

20 안지환 ; 김형석 ; 조영도, "Precipitation characteristics of heavy metal ions in coal mine drainage" 20 (20): 125-134, 2007

21 U.S. EPA, "Permeable Reactive Barriers for Inorganics" 1-55, 2000

22 Fruchter, J., "Peer reviewed : In-situ treatment of chromiumcontaminated groundwater" 36 (36): 464A-472A, 2002

23 McGinty, J., "Nucleation and crystal growth in continuous crystallization, handbook of continuous crystallization" 1-16, 2020

24 Aspillaga, L., "Nucleation and crystal growth : Recent advances and fufture trends" 56 : 22-, 2023

25 Estay, H., "Metal sulfide precipitation : Recent breakthroughs and future outlooks" 11 (11): 1385-, 2021

26 Zhao, X., "Mathematical estimation of heavy metal accumulations in helianthus annuus L. with a sigmoid heavy metal uptake model" 220 : 965-973, 2019

27 Yahikozawa, K., "Kinetic studies on the lime sulfurated solution(Calcium Polysulfide)process for removal of heavy metals from wastewater" 51 (51): 613-617, 1978

28 U.S. DOE, "Internet ref"

29 Lewis, A. E., "Industrial crystallization: Fundamentals and Applications" 2015

30 Wright, K. E., "Inducing mineral precipitation in groundwater by addition of phosphate" 12 : 8-, 2011

31 Zhang, X., "In-depth characterization of secondary phases in Cu2ZnSnS4 film and its application to solar cells" 9 (9): 855-, 2019

32 Yin, Y., "In situ chemical treatment"

33 이상우 ; 김정진 ; 박미정 ; 이상환 ; 김순오, "Human risk assessment of arsenic and heavy metal contamination and estimation of remediation concentration within abandoned metal mine area" 28 (28): 309-323, 2015

34 최현미 ; 이진용, "Green remediation : Choice for low CO2 emission in soil and groundwater remediation" 14 (14): 11-17, 2009

35 Gross, S., "Functionalisation of colloidal transition metal sulphides nanocrystals : A fascinating and challenging playground for the chemist" 7 (7): 110-, 2016

36 Hillis, B. G., "From rate measurements to mechanistic data for condensed matter reactions : A case study using the crystallization of [Zn(OH2)6][ZnCl4]" 7 (7): 11-, 2017

37 Zhong, L., "Foam delivery of calcium polysulfide to the vadose zone for chromium(VI)immobilization : A laboratory evaluation" 8 (8): 976-985, 2009

38 U. S. EPA, "Field applications of in situ remediation technologies:Permeable reactive barriers" DIANE Publishing 1999

39 Huang, C. Y., "Feasibility of remediation lead, Nickel, Zinc, Copper, and cadmium-contaminated groundwater by calcium sulfide" 13 (13): 2266-, 2021

40 Fantauzzi, M., "Exploiting XPS for the identification of sulfides and polysulfides" 5 : 75953-75963, 2015

41 Luther, G. W., "Evidence for aqueous clusters as intermediates during zinc sulfide formation" 63 (63): 3159-3169, 1999

42 Hu, S., "Evaluation of remediation of Cr(VI)-contaminated soils by calcium polysulfide : Long-term stabilization and mechanism studies" 790 : 148140-, 2021

43 Mpouras, T., "Evaluation of calcium polysulfide as a reducing agent for the restoration of a Cr(VI)-contaminated aquifer" 105 : 45-52, 2020

44 정문영 ; 정명채, "Evaluation and management method of environmental contamination from abandoned metal mines in Korea" 43 (43): 283-394, 2006

45 Zhao, X., "Estimation of the seedling vigor index of sunflowers treated with various heavy metals" 7 (7): 353-, 2016

46 Migdisov, A. A., "Estimates of the second dissociation constant of H2S from the surface sulfidation of crystalline sulfur" 66 (66): 1713-1725, 2002

47 Kapusta, P., "Effects of heavy metal pollution from mining and smelting on enchytraeid communities under different land management and soil conditions" 536 (536): 517-526, 2015

48 Qian, Y., "Crystallization of nanoparticles induced by precipitation of trace polymeric additives" 12 (12): 2767-, 2021

49 Leite, E. R., "Crystallization and Growth of Colloidal Nanocrystals" Springer 2011

50 Aratani, T., "Continuous Removal of Heavy metals by the Lime Sulfurated Solution(Calcium Polysulfide)Process" 52 (52): 218-222, 1979

51 Sankhla, M. S., "Contaminant of heavy metals in groundwater & its toxic effects on human health & environment" 18 (18): 555996-, 2019

52 EFSA, "Conclusion on the peer reviewed of the pesticide risk assessment of the active substances lime sulfur" 8 (8): 1890-, 2010

53 Wielinski, J., "Characterizing the stoichiometry of individual metal sulfide and phosphate colloids in soils, sediments, and industrial processes by inductively coupled plasma time-of-flight mass spectrometry" 58 : 12113-12122, 2024

54 Dahlawi, S. M., "Calcium polysulphide, its applications and emerging risk of environmental pollution—A review article" 24 : 7842-7856, 2017

55 Chrysochoou, M., "Calcium polysulfide treatment of Cr(VI)-contaminated soil" 179 (179): 650-657, 2010

56 Kubier, A., "Cadmium in Soils and Groundwater : A Review" 108 : 104388-, 2019

57 Kotula, P. G., "Automated analysis of SEM X-ray spectral images : A powerful new microanalysis tool" 9 (9): 1-17, 2003

58 Go, H. W., "Application of Calcium polysulfide in various media for remediation of high concentration heavy metal contaminated groundwater" Hanbat National University 2023

59 Cui, Y., "Advanced XPS-based techniques in the characterization of catalytic materials : A mini-review" 14 (14): 595-, 2024

60 이기민 ; 김규리 ; 최성규 ; 이태진, "A study on adsorption of heavy metals with zeolite and FeS Media" 42 (42): 349-359, 2020

61 Chrysochoou, M., "A kinetic study of Cr(VI)reduction by calcium polysulfide" 409 (409): 4072-4077, 2011

62 Chrysochoou, M., "A comparative evaluation of hexavalent chromium treatment in contaminated soil by calcium polysulfide and green-tea nanoscale zerovalent iron" 201-202 : 33-42, 2011