Instrumental Techniques for Environmental Investigations Methodological Guide

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2 JOINT OPERATIONAL PROGRAMME ROMANIA-UKRAINE-REPUBLIC OF MOLDOVA Common borders. Common solutions PROJECT MIS ETC 1676 Instrumental Techniques for Environmental Investigations Methodological Guide Editor Prof.dr. habil.antoaneta Ene Tehnopress Iași, 2015

3 Address of the Editor: Department of Chemistry, Physics and Environment Faculty of Sciences and Environment Dunarea de Jos University of Galaţi 47 Domneasca St., Galaţi , Romania List of contributor authors: Simona CONDURACHE-BOTA Ch. 1 Mirela PRAISLER, Steluta GOSAV, Nicoleta PADURARU & Atanasia STOICA MANDRU Ch. 2 Antoaneta ENE Ch. 3 Oleg BOGDEVICH & Antoaneta ENE Ch. 4 Methodological Guide was financially supported by: Project MIS ETC JOP Romania-Ukraine-Republic of Moldova

4 Instrumental Techniques forenvironmentalinvestigations Methodological Guide Antoaneta Ene (Editor) Common borders. Common solutions Project MIS ETC 1676 CONTENTS FOREWORD. 5 Chapter 1. UV-VIS spectroscopic methods for environmental analysis... Simona CONDURACHE-BOTA Introduction to the principles of spectroscopy Light and matter fundamentals Basic terms in spectroscopy The energy levels theory an introduction Quantum theory for the energy of atoms and molecules. Basics for the theory of orbitals Different absorbing species. The chromophores Principles of UV-VIS spectroscopic measurements UV-VIS spectral instrumentation Essential issues concerning the components of an UV-VIS spectrometer Practical recommendations for UV-VIS analysis. Pros and cons for this technique Environmental applications for UV-VIS spectrometry... References Chapter 2. Infrared spectroscopy Mirela PRAISLER, Steluta GOSAV, Nicoleta PADURARU, Atanasia STOICA MANDRU Introduction Types of vibrations IR spectrometers Fourier Transform IR spectrometers (FTIR) Applications of FTIR spectroscopy in pollutant measurements... References

5 Instrumental Techniques forenvironmentalinvestigations Methodological Guide Antoaneta Ene (Editor) Common borders. Common solutions Project MIS ETC 1676 Chapter 3. X-ray fluorescence technique Antoaneta ENE Principles of X-ray fluorescence technique Emission of characteristic X rays Auger process. Fluorescence yield Excitation sources for characteristic X rays Excitation with the X ray tube Excitation with radiations emitted by radioisotopes Detection of X rays X rays spectrometry Spectrometers with wavelength dispersion (WDS) Spectrometers with energy dispersion (EDS) Qualitative and quantitative XRF analysis Qualitative analysis Quantitaive analysis Applications of XRF technique in environmental studies References Chapter 4. Gas chromatography technique in environmental analyses.. Oleg BOGDEVICH, Antoaneta ENE Introduction to chromatography Chromatography columns Chromatography parameters Instruments specific to chromatographic methods GC system Detectors for GC method 4.3. Extraction methods in gas chromatography 4.4. Cleanup procedures for organic analysis Qualitative and quantitative analysis of organoclorine pesticides and polycyclic aromatic hydrocarbons using GC-ECD and GC-MS methods.. References

6 TehniciInstrumentale pentruinvestigații demediu Ghid Metodologic Antoaneta Ene (Editor) Common borders. Common solutions Project MIS ETC 1676 CUPRINS PREFAȚĂ 113 Capitolul 1. Metode spectrale în UV-VIZ pentru analize de mediu Simona CONDURACHE-BOTA Introducere în principiile spectroscopiei Lumină și materie noțiuni fundamentale Termeni de bază în spectroscopie Introducere în teoria nivelurilor energetice Teoria cuantică pentru energia atomilor și moleculelor. Bazele teoriei orbitalilor Diferite specii absorbante. Cromoforii Principiile măsurărilor spectrale în UV-VIZ Aparatură spectrală în UV-VIZ Chestiuni esențiale privind părțile componente ale unui spectrometru UV-VIZ Recomandări practice pentru analiza UV-VIZ. Avantaje și dezavantaje ale acestei tehnici Aplicații de mediu ale spectrometriei UV-VIZ... Bibliografie Capitolul 2. Spectroscopia în infraroșu Mirela PRAISLER, Steluta GOSAV, Nicoleta PADURARU, Atanasia STOICA MANDRU Noțiuni generale Tipuri de vibrații Spectrometre IR Spectrometrul IR cu transformată Fourier Aplicații ale spectroscopiei FTIR în analize de mediu Bibliografie

7 TehniciInstrumentale pentruinvestigații demediu Ghid Metodologic Antoaneta Ene (Editor) Common borders. Common solutions Project MIS ETC 1676 Capitolul 3. Tehnica fluorescenţei de raze X.... Antoaneta ENE 3.1. Principiile tehnicii fluorescenţei de raze X Emisia radiaţiilor X caracteristice Procesul Auger. Randamentul de fluorescenţă Surse de excitare a radiaţiilor X caracteristice Excitarea cu ajutorul tubului generator de raze X Excitarea cu radiaţii emise de radioizotopi Detecția radiațiilor X Spectrometria radiaţiilor X Spectrometre cu dispersie după lungimea de undă (WDS) Spectrometre cu dispersie după energie (EDS) Analiza XRF calitativă şi cantitativă Analiza calitativă Analiza cantitativă Aplicaţii ale tehnicii fluorescenţei de raze X în studii de mediu Bibliografie Capitolul 4. Technica cromatografiei de gaze în analize de mediu... Oleg BOGDEVICH, Antoaneta ENE 4.1. Introducere în cromatografie Coloane cromatografice Parametri cromatografici Instrumente specifice metodelor cromatografice Sistemul GC Detectori utilizați în metoda GC Metode de extracție în cromatografia gazoasă Proceduri de purificare pentru analiza organică Analiza calitativă și cantitativă a pesticidelor organoclorurate și a hidrocarburilor aromatice policiclice folosind metodele GC-ECD și GC-MS Bibliografie

8 Instrumental Techniques for Environmental Investigations Methodological Guide Antoaneta Ene (Editor) Common borders. Common solutions Project MIS ETC 1676 FOREWORD The whole spectrum of environmental issues of our time can only be considered and solved based on both fundamental and applied scientific approach. The diversification of environmental problematics and the need for a monitoring as efficiently have imposed the elaboration of several analysis methods characterized by a high sensibility, selectivity, reproducibility and precision. This methodological guide is published in the frame of the project Crossborder interdisciplinary cooperation for the prevention of natural disasters and mitigation of environmental pollution in Lower Danube Euroregion MIS ETC 1676, which has been carrying out during by a team of researchers from Romania, the Republic of Moldova and Ukraine. The project targeted the enforcing of cross-border cooperation aiming to elaborate long-term solution for pollution mitigation, sustainable development and emergency preparedness in the Lower Danube Euroregion. In order to fulfil the project goal, a range of specific objectives were set: integration of the capacities and expertise of the partner institutions to assess the cross-border impact of the environmental problems in the Lower Danube River basin; creation of a mechanism capable to provide the scientific support for decision makers for the elaboration of policy related to the prevention of the negative impact of potential natural and anthropogenic accidents in the region; raising the level of awareness of the population in the region regarding the environmental issues with cross-border impact; encouraging the involvement of young researchers, undergraduate, master and PhD students in cross-border environmental research; improvement of ecological situation in Lower Danube Euroregion. The project has allowed creating by the partner institutions of an international interdisciplinary network (INPOLDE), designed to accumulate background data, conduct complex environmental investigations in border areas, assess the environmental impact and, finally, to offer a better scientific support to the regional monitoring programs. 5

9 Instrumental Techniques for Environmental Investigations Methodological Guide Antoaneta Ene (Editor) Common borders. Common solutions Project MIS ETC 1676 The work Instrumental Techniques for Environmental Investigations Methodological Guide is part of a series of works to be edited under the abovementioned project, which is dedicated to the methodological aspects of research on various environmental components, by applying modern analytical techniques in assessing the level of environment pollution. It is based on an extensive personal experience of the authors, and the good international practices in studying the physico-chemical parameters of various environmental factors. The overall objective of this guide is to introduce an overview on the fundamentals of analysis for students of the specializations of bachelor and master of science and environmental engineering, as well as specialists, engineers or researchers in physics, chemistry, biology, geology, environmental sciences, food engineering, who are involved in different research stages and analytical determinations, university teachers, postgraduates etc. The monograph is divided into four chapters and describes the theoretical principles, peculiarities, specific instrumentation and environmental applications of the most important analytical instrumental techniques: X-ray fluorescence (XRF); UV-Vis spectroscopy; IR and FT-IR spectroscopy and gas chromatography. The techniques described have been used in partner institutions for analysis of environmental samples in the frame of the research project funded by, in complementarity with other instrumental techniques such as atomic absorption spectroscopy (AAS) and high performance liquid chromatography (HPLC), described in other works developed within the project. The editor and the authors thank this way Mrs. Prof.dr.habil. Elena Zubcov and Mr. Dr. chem. Yuriy Denga, project coordinators of partner institution, for reviewing the work. Galati, December 2015 Prof.dr.habil. Antoaneta Ene - Editor 6

10 Chapter 3 X-ray Fluorescence Technique Antoaneta Ene 3.1. Principles of X-ray fluorescence technique Emission of characteristic X rays Electrons of an atom ocupy levels with well determined energies, E n, which differ from one element to another, according to Bohr relation for the atom with many electrons: Rhc E Z 2 n n2 (3.1) where Z is the atomic number of the element; R Rydberg constant; - shielding constant; h Planck constant; n main quantum number. If an electron existing on a layer with the main quantum number m is ejected under the action of a quanta of sufficiently high energy, the atom is ionized and the hole formed in the respective layer can be filled by another electron from a layer located further from the nucleus, with the main quantum number n (n>m). In conformity with the energy conservation law, a photon will be emitted with an energy belonging to the X-rays domain, E X = E n - E m, corresponding to the difference between the energies of the involved levels, named characteristic X-ray or fluorescent X-ray. A.Ene Faculty of Sciences and Environment, Chemistry, Physics and Environment Department, Dunarea de Jos University of Galati, Romania A. Ene (editor), Instrumental Techniques for Environmental Investigations Methodological Guide Dunarea de Jos University of Galati, Romania aene@ugal.ro 61

11 Antoaneta Ene References [1] Bertin E.P., Principles and Practice of X-Ray Spectrometric Analysis, Plenum Press, New York, [2] Nat A., Fizică atomică şi nucleară, Universitatea Galaţi, [3] Ene A., Study of the microelements composition of raw materials, agglomerates and related finished iron and steel products using atomic and nuclear methods. Ph.D. Thesis, Faculty of Physics, University of Bucharest, Romania, [4] Ene A., Metode radiometrice de analiză multielementală, Editura Cartea Universitară, Bucureşti, [5] Ene, A., Tehnici radiometrice de analiză și control, Editura Fundației Universitare Dunărea de Jos din Galați, Galați, [6] Ene A., Pantelica A., Tehnici analitice atomice și nucleare utilizate în monitorizarea mediului (Atomic and nuclear analytical techniques used in environmental monitoring; in Romanian), Galati University Press, Galati, [7] Jenkins R., DeVries J.L., Practical X-ray Spectrometry, 2nd ed., Springer-Verlag, [8] Muhin K.N., Fizică nucleară experimentală, vol. 1, Ed. Tehnică, Bucureşti, [9] Năşcuţiu T., Metode radiometrice de analiză, Ed. Academiei, Bucureşti, [10] Tertian R., Claisse F., Principles of Quantitative X-ray Fluorescence Analysis, Heyden, London, [11] Williams K.L., Introduction to X-ray Spectrometry, Allen & Unwin, [12] Statham P J., A comparative study of techniques for the quantitative analysis of X-ray spectra obtained with a Si(Li) detector, X-Ray Spectrometry 5, 16, [13] Jenkins R., An introduction to X ray spectrometry, Heyden, London, New York, Rheine, [14] Liebhafsky H.A., Pfeiffer H.G., Winslow E.H.. Zemany P.D., X-rays, Electrons and Analytical Chemistry, John Wiley & Sons, [15] Scott V.D., Love G., Quantitative Electron Probe Microanalysis, Ellis Horward Ltd., Chichester, [16] Newbury D. E., Joy D. C., Echlin P., Fiori C.E., Goldstein J. I., Advanced Scanning Electron Microscopy and X-Ray Microanalysis, Plenum Press, New York, [17] Ene A., Nat A., Îndrumar de laborator de fizică atomică şi nucleară, Universitatea Dunărea de Jos Galaţi, [18] International Tables for X-ray Crystallography, vol. 4, Kynoch Press, Birmingham, [19] Gazea (Ene) A., Metode atomice şi nucleare de analiză aplicate în studii de poluare, Lucrare de disertaţie, Universitatea Dunărea de Jos Galaţi, [20] Broll N., Tertian R., X-Ray Spectrometry 12, 1, [21] Baptista G.B., Montenegro E.C., Barros Leite C.V., Pashoa A.S., J. Radioanal. Chem. 60, 227, [22] Van Grieken R., Markowicz A., Handbook of X-Ray Spectrometry, Methods and Techniques, Marcel Dekker Inc., New York,

12 X-ray Fluorescence Technique [23] Ene A., Applications of high sensitivity analytical techniques in industry and pollution management for trace chemical composition characterization of complex samples, Habilitation Thesis, Universitatea Dunarea de Jos din Galati, [24] Evans Analytical Group, [25] IAEA Vienna, XRF Newsletter 3, [26] [27] Ene A., Bosneaga A., Georgescu L., Determination of heavy metals in soils using XRF technique, Rom. Journ. Phys. 55 (7-8), 815, [28] Stihi C., Popescu I.V., Gheboianu A., Frontasyeva M., Ene A., Dima G., et al., Mineral content of native vegetables obtained by energy dispersive X- ray fluorescence spectrometry, Journal of Science and Arts, Year 8, 2(9), 331, [29] Stihi C., Radulescu C., Busuioc G., Popescu I.V., Gheboianu A., Ene A., Studies on accumulation of heavy metals from substrate to edible wild mushrooms, Rom. Journ. Phys. 56(1-2), 257, [30] Ene A., Stihi C., Popescu I.V., Gheboianu A., Bosneaga A., Bancuta I., Comparative studies on heavy metal content of soils using AAS and EDXRF atomic spectrometric techniques, Annals Univ. Dunarea de Jos Galati, Fasc. II - Mathematics, Physics, Theoretical Mechanics, Year I(XXXII), 51, [31] Ene A., Pantelica A., Freitas M. C., Bosneaga A., EDXRF-INAA analysis of soils in the vicinity of a metallurgical plant, Rom. Journal Phys. 56(7-8), 993, [32] Ene Antoaneta, Frontasyeva M.V., Popescu I.V., Stihi C., Ene Andreea, Drasovean R., Chelarescu E.D., Applications of INAA and X-ray based techniques for trace element analysis in materials and environmental sciences, 21st International Seminar on Interaction of Neutrons with Nuclei (ISINN-21), Alushta, Ukraine, May 20-25, 2013, Abstracts of the Seminar, Dubna JINR, 2013, p.31. [33] Cojocaru V., Pantelica A., Pincovschi E., Georgescu I.I., EDXRF versus INAA in pollution control of soil, J. Radioanal. Nucl. Chemistry 268(1), 71, [34] Pantelica A., Cercasov V., Steinnes E., Bode P., Wolterbeek B, Investigation by INAA, XRF, ICP-MS and PIXE of air pollution levels at Galati (siderurgical site). In: 4 th National Conference of Applied Physics, Galati, Romania, Sept , 2008, Book of abstracts (Ene A., ed.), Galati University Press, Galati, [35] Ene A., Modern techniques used in environmental investigations, 6 th scientific seminar of INPOLDE interdisciplinary network, Project MIS ETC 1676, Chisinau, October 5-6, [36] Tallandini L., Giacibini F., Turchetto M., Galassini S., Liu Q.X., et al., Naturally occuring levels of elements in fishes as determined by PIXE and XRF methods, Nucl. Instr. and Meth. B40/41, 630, [37] Pantelica A., Ene A., Georgescu I.I., Instrumental neutron activation analysis of some fish species from Danube River in Romania, Microchem. J. 103, 142, [38] Pantelica A., Freitas M.C., Ene A., Steinnes E., Soil pollution with toxic trace elements in selected Romanian sites studied by instrumental neutron activation analysis, Radiochimica Acta 101, 45, [39] Ene A., Popescu I.V., Stihi C., Applications of proton-induced X-ray emission technique in materials and environmental science, Ovidius Univ. Annals of Chemistry, 20(1), 35,

13 Antoaneta Ene [40] Ene A., Popescu I.V., Stihi C., Gheboianu A., Pantelica A., Petre C., PIXE analysis of multielemental samples, Rom. Journ. Phys. 55 (7-8), 806, [41] Ene A., Pantelica A., Gugiu M., Calinescu C.I., Fluerasu D., Elemental contents in Danube River water in Galati region determined by PIXE, 12 th International Balkan Workshop on Applied Physics, July 06-08, Constanta, Romania, [42] Pantelica A., Ene A., Gugiu M., Ciortea C., Constantinescu O., PIXE analysis of some vegetal species, Rom. Rep. Phys. 63(4), 997, [43] Maenhaut W., Recent advances in nuclear and atomic spectrometric techniques for trace element analysis. A new look at the position of PIXE, Nucl. Instr. and Meth. B49, 518, [44] Zubcov, E., Zubcov, N., Ene, A., Biletchi, L., Assessment of copper and zinc levels in fish from freshwater ecosystems of Moldova, Environmental Science and Pollution Research 19(6), 2238, [45] Zubcov, E., Zubcov, N., Ene, A., Biletchi, L., Trace metals in fish from freshwater ecosystems of Lower Prut natural reserve, 14 th International Balkan Workshop on Applied Physics (IBWAP 2014), Constanta, Romania, July 2-4,