Analysis and Correlatıon of Element Concentratıons of Marine Sediments between Silivri (İstanbul) and Dardanelles by ICP-OES and LIBS Methods

Abstract

In this work, the LIBS (Laser Induced Breakdown Spectroscopy) and ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometer) technique applied to the determination of total concentration of some elements (Fe, Zn, Al, Mn, Co, Cr, Cu, Ni, Na, Mg, K, Ca) derived from soil samples of Marmara Sea. To support to the technique, LIBS data were compared with data have been obtained on the same soil samples by application of Conventional Inductively Coupled Plasma Spectroscopy (ICP-OES). The similarity of results obtained between the two sets of data suggested the potential applicability of the LIBS technique to the measurement of elements in soils. According to the study, it has been seen that the elements determined by ICP-OES analysis also determined by LIBS method. It has the advantages of being faster than other traditional methods, being portable, having low analysis costs, not being damaged and re-used during the analysis and short preparation period. However, the LIBS method is an important and practical technique for the determination of elements of natural and anthropogenic origin. In the analysis made by ICP-OES method, the amounts of the elements in ppm are determined, while the results of LIBS analysis show the presence of the element only in %. According to LIBS method, Zn, Mn, Co, Cr and Cu concentrations vary according to each region. In this study, according to ICP-OES analysis, Zn (42.2-111.7 ppm), Mn (163.2-581.1 ppm), Co (37.14-65.87 ppm), Cr (42.5-112.6 ppm), Cu (5.71-24.33 ppm), Ni ( 98.20-175.55 ppm), Al (16568.8-24850.9 ppm), Fe (20936.9-37397.9 ppm), Na (5223.4-12384.7), Mg (4800.4-7385.3 ppm), K (3290.8-5582.0) and Ca (42405.2-154577.0 ppm) ). LIBS analysis results showed that parallels Zn (0-22%), Mn (0-28%), Co (0-21%), Cr (0-23%), Cu (0-19%), Ni (%) 0-2), Al (67-78%), Fe (94-95%), Na (70-87%), Mg (82-90%), K (85-94%), Ca (66-%) 80). The LIBS method is an important technique for identifying elements enriched with anthropogenic factors and elements originating from natural processes. The LIBS method can be used to determine the source of elements in marine or terrestrial environments. In addition, the LIBS method; It has also shown important results in the determination of toxic elements such as Mn, Cr, Co and Cu which increase in marine sediment by anthropogenic factors.

Keywords

• LIBS
• ICP-OES
• Toxic Element
• Marmara Sea
• Çanakkale Strait

Silivri (İstanbul) ve Çanakkale Boğazı Arasındaki Denizel Sedimanların Element Konsantrasyonlarının ICP-OES ve LIBS Yöntemleri İle Analizi ve Korelasyonu

Abstract

Bu çalışmada Marmara Denizi deniz sedimanlarının toksik element (Fe, Zn, Al, Mn, Co, Cr, Cu, Ni, Na, Mg, K, Ca) konsantrasyonları LIBS (Lazer İndüklenmiş Plazma Spektroskopisi) ve ICP-OES (İndüktif Eşleşmiş Plazma-Optik Emisyon Spektrometresi) teknikleri ile belirlenmiştir. LIBS tekniği ile elde edilen sonuçların desteklenmesi için aynı sediman örnekleri ICP-OES yöntemi ile de analiz edilmiştir. İki yöntemden de elde edilen sonuçlar karşılaştırıldığında LIBS yönteminin sediman örnekleri üzerinde kullanılabilirliği görülmüştür. Çünkü ICP-OES ile elde edilen sonuçlar ile LIBS ile elde edilen sonuçlar birbirleri ile paralellik göstermektedir. Geleneksel diğer tüm yöntemlerden hızlı sonuç vermesi, taşınabilir olması, analiz maliyetlerinin düşük olması, kullanılan örneğin analiz sırasında zarar görmemesi ve tekrar kullanılabilmesi ve ön hazırlık sürecinin kısa olması gibi avantajları vardır. Bununla birlikte LIBS yöntemi, doğal ve antropojenik kökenli elementlerin belirlenmesi için önemli ve pratik bir tekniktir. Bu metot günümüzde gıda, çevre, sağlık ve tekstil alanlarında kullaılan yeni bir yöntemdir. ICP-OES yöntemiyle yapılan analiz sonuçlarında elementlerin miktarları ppm cinsinden, LIBS yöntemiyle elde edilen analiz sonuçları ise sadece % cinsinden verilmektedir. Bu çalışmada ICP-OES analizi sonucuna göre Zn (42.2-111.7 ppm), Mn (163.2-581.1 ppm), Co (37.14-65.87 ppm), Cr (42.5-112.6 ppm), Cu (5.71-24.33 ppm), Ni (98.20-175.55 ppm), Al (16568.8-24850.9 ppm), Fe (20936.9-37397.9 ppm), Na (5223.4-12384.7), Mg (4800.4-7385.3 ppm), K (3290.8-5582.0), Ca (42405.2-154577.0 ppm) olarak elde edilmiştir. LIBS analiz sonuçlarıda; Zn (% 0-22), Mn (%0-28), Co (%0-21), Cr (%0-23), Cu (%0-19), Ni (%0-2), Al (%67-78), Fe (%94-95), Na (%70-87), Mg (%82-90), K (%85-94), Ca (%66-80) olarak elde edilmiştir. Sonuçlar incelendiğinde LIBS yönteminin; Antropojenik faktörlerle deniz sedimentinde artan Mn, Cr, Co ve Cu gibi toksik elementlerin belirlenmesinde önemli sonuçlar verdiği görülmüştür. Denizel veya karasal ortamlardaki elementlerin kaynağını belirlemek için LIBS metodu, ICP-OES metodu ile paralellik gösterdiği için kullanılabilir.

Keywords

• LIBS
• ICP-OES
• Toksik Element
• Marmara Denizi
• Çanakkale Boğazı

References

1. Senesi, G.S., Baldassarre, G., Senesi, N. & Radina, B. (1999). Trace element inputs into soils by anthropogenic activities and implications for human health. Chemosphere, 39, 343–377.
2. Rusak D. A., Castle B.C., Smith B.W. & Winefordner J.D. (1997). Fundamentals and Applications of Laser Induced Breakdown Spectroscopy. Crit. Rev. Anal. Chem. 27. 257-290.
3. Song K., Lee Y. & Sneddon J. (1997). Applications of Laser Induced Breakdown Spectroscopy. Appl. Spectrosc. Rev. 32 (3). 183-235.
4. Velioğlu M. H., Sezer B., Bilge G., Baytur S.E. & Boyacı I.H.(2018). Identification of Offal Adulteration in Beef by Laser Induced Breakdown Spectroscopy. Meat Science. 138. 28-33.
5. Christoper, D. R. & Scott, G. R. (2003). Laser-induced Breakdown Spectrocopy fort he Detection of Gunshot Residues on the Hands of a Shooter. Applied Optics. 42.30.
6. Almessiere, M.A., Altuwiriqi, R., Gondal, M.A., Aldakheal, R.K. & Alotaibi, H.F. (2018). Qualitative and quantitative analysis of human nails to find correlation between nutrients and vitamin D deficiency using LIBS and ICP-AES. Talanta. 185.61-70.
7. Anzano, J.M., Villoria, M.A., Ruíz-Medina, A. & Lasheras, R.J. (2006). Laser-induced breakdown spectroscopy for quantitative spectrochemical analysis of geological materials: Effects of the matrix and simultaneous determination. Analytical Chimica Acta 575 (2): 230-235.
8. Samek, O., Krzyžánek, V., Beddows, D.C., Telle, H.H., Kaiser, J. & Liška, M. (2001). In: material identification using laser spectroscopy and pattern recognition algorithms. International Conference on Computer Analysis of Images and Patterns, Springer, Berlin: 443–450.

9. Vadillo, J.M., Cardell, K., Cremers, D.A. & Laserna, J.J. (1999) . Rapid screening method for heavy metals in contaminated soils using LIBS. Quimica Analytica, 18: 169- 174.
10. Yümün, Z. U., Kam, E. & Once, M. (2019). Analysis of Toxic Element with Icp-Oes and Libs Methods in Marine Sediments Around the Sea of Marmara in Kapidağ Peninsula. Journal of Engineering Technology and Applied Sciences 4 (1). : 43-50.
11. Yümün, Z.U. (2017). The effect of heavy metal pollution on foraminifera in the western Marmara Sea (Turkey). Journal of African Earth Science.129. 346-365.
12. Yümün, Z.U. & Once, M. (2017). Monitoring heavy metal pollution in foraminifera from the Gulf of Edremit (northeastern Aegean Sea) between Izmir, Balıkesir and Çanakkale (Turkey). Journal of African Earth Sciences.
13. Kam, E. & Once, M. (2016). Pollutıon Potentıal Of Heavy Metals In The Current Sea Sedıments Between Bandırma (Balıkesir) And Lapseki (Çanakkale) In The Marmara Sea. Journal of Engineering Technology and Applied Sciences. 3.141-148.
14. Barbini, R., Colao, F., Fantoni, R., Palucci, A. & Capitelli, F., (1999). Application of laser induced breakdown spectroscopy to the analysis of metals in soils. Appl. Phys. A 69: S175–S179 Supp. l.
15. Yang, N. (2009). Elemental Analysis of Soil Using Laser-Induced Breakdown Spectroscopy . University of Tennessee. Master Theses.
16. Pandhija, S., Rai, N.K., Rai, A.K. & Thankur, S.N. (2010). Contaminant Concentration in Enviromental Samples Using LIBS and CF-LIBS. Applied Physics B. 98. 231-241.
17. Yümün, Z.U. (2016). The Effects of Heavy Metal Concentrations in The Çanakkale Strait (Turkey): Morphological Differences in The Holocene Foraminiferal Assemblages. Journal of Engineering Technology and Applied Sciences. 1(2). 77-88.
18. Schecter, I. (1997). Laser Induced Plasma Spectroscopy. A Rewiev of Recent Advances. Rev. Anal. Chem. 16 (3). 173-298.