Experience of using neutron activation analysis on mineral and biological samples: environmental and medical studies. ANA PANTELICĂ “Horia Hulubei” National Institute for Physics and Nuclear Engineering, P.O. Box MG-6. 76900 Bucharest- Măgurele, Romania. Introduction.
“Horia Hulubei” National Institute for Physics and Nuclear Engineering, P.O. Box MG-6. 76900 Bucharest- Măgurele, Romania
Main achievements from environmental and medical studies, based on a thirty-year experience in applying Instrumental Neutron Activation Analysis (INAA) on different mineral and biological samples at “Horia Hulubei” National Institute of Physics and Nuclear Engineering in Bucharest are presented.
Neutron irradiation was carried out at the VVR-S reactor in Bucharest (short and long-term irradiation) and TRIGA reactor in Pitesti (long-term irradiation) after VVR-S reactor shutdown in 1997, at a neutron fluence rate of 2.3·1012 cm-2·s-1, and 1-3 ·1013 cm-2·s-1, respectively.
Elements investigated by INAA on environmental samples: Ag, As, Au, Ba, Br, Ca, Cd, Ce, Co, Cr, Cs, Eu, Fe, Hf, Hg, K, La, Lu, Mo, Na, Nd, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, U, W, Yb, Zn and Zr by long-term irradiation, and Al, Cl, Cu, Dy, I, Mg, Mn, Ti and V by short-term irradiation (44 elements).
As standards, reference materials such as W-1 and GSP rocks, IAEA-Soil 7, MA-M-2/TM mussel, MA-B-3/TM fish, IAEA-140 sea weed, WTM water sludge and EOP fly coal ash from the Institute of Radioecology and Applied Nuclear Techniques Kosice (Slovakia), as well as chemical compounds of Al, Ca, Mg, Mn and V were used.
Monostandard method was in addition applied in some cases (e.g. Ti and Sr analytes, with Cl and Zn as monostandards, respectively).
Quality control in INAA was periodically checked on various mineral and biological Reference Materials from intercomparison runs (major, minor and trace element certification).
Introduction (continued) and biological samples: environmental
- GAMMAW program for automatic and semi-automatic spectra processing
[W. Westmeier. GAMMAW. Version 17.11. Gesellschaft für Kernspektrometrie mbH Consulting, Software, Instruments, Ebsdorfergrund-Mölln, 1996].
- Program to determine concentration values as well as the corresponding statistical counting errors in relative INAA method.
I. Danube River and Black Sea and biological samples: environmental pollution study
- marine algae (e.g. Enteromorpha linza as Clorophytes and Ceramium rubrum as Rhodophytes),
- marine molluscs (Mytilus galloprovincialis and Mya arenaria), polychaete (Melina palmata), and crustacea (Mesopodopsis slabberi Van Bened of Mysidacea specie)
- Danube River fish (Alburnus alburnus, Acipenser ruthenus, Carasius auratus, Cyrinus carpio, Ctenopharingodon idaella, Perca fluviatilis, Rutilus rutilus,and Silurus glanis).
1. Air pollution (PM10) at Bucharest-Magurele and Stuttgart-Hohenheim was in parallel investigated, during one year (1 Nov. 1993 and 31 Oct. 1994), by a weekly collection of airborne particulate matter on filters.
(German-Romanian BMBF Joint Project X055.1/1993-1995 Collaborations with Dr. V. Cercasov and Prof. H. Schreiber, and Institute of Physics and Meteorology, Univ. Hohenheim in Stuttgart, Germany}.
2. The suitability of three lichen species as bioaccumulators of trace elements from atmospheric deposition in zones with different pollution levels and different climates in Germany, Italy and Romania (two locations in every country - Bucharest and Târgoviste in Romania). The investigated species Cetraria islandica, Evernia prunastri and Ramalina farinacea were transplanted from a non-polluted Prealps area in Italy and exposed during 2, 4, 6 and 12 months.
(German-Romanian BMBF Joint Project RUM-020-96/1995-1998 - Dr. V. Cercasov, Univ. Hohenheim in Stuttgart, Germany and Prof. G. Caniglia, Univ. Padua, Italy).
3. Characterization of air pollution at six locations with different types of industrial activity (Afumati, Baia Mare, Copsa Mica, Deva, Galati, Oradea) and a background site (Fundata) in Romania using transplant lichen bioaccumulators (Evernia prunastri and Pseudevernia furfuracea exposed during 6 and 12 months), bulk (wet and dry) deposition, and airborne particulate matter collection on filters.
ICA1-CT-2000-70023 Center of Excellence EU Project IDRANAP (InterDisciplinary Research and Applications based on Nuclear and Atomic Physics, WP2), during 2000-2004
Collaboration with Univ. Hohenheim in Stuttgart, Germany (Dr. V. Cercasov), IRI TU Delft, The Netherlands (Dr. B. Wolterbeek and Dr. P. Bode) and Norwegian Univ. Trondheim, Norway (Prof. E. Steinnes).
Comparison of elemental concentrations in Pseudevernia furfuracea before exposure (“zero level”) and after 12- months exposure at Copsa Mica (non-ferrous industry), Deva (coal-fired power plant and cement industry) and Galati (metallurgical industry)
a) Anthropogenic contribution:
Copşa Mică >> Baia Mare > Afumaţi, Galaţi, Deva > Oradea.
b) Crustal contribution:
Galaţi > Afumaţi > Copşa Mică > Deva > Baia Mare, Oradea.
The anthropogenic pollution was mainly due to the following types of industrial activities: non-ferrous (Copşa Mică), metallurgic (Galaţi), coal power plant and cement factory (Deva), non-ferrous mining (Baia Mare), agriculture and mixed industry (Afumaţi, near Bucharest), traffic and mixed industry (Oradea).
- soil and vegetation (tree leaves, potato, carrot, and corn) collected at different distances from the plant;
- workplace air (airborne particulate matter and dust deposition) and
- hair and nail biosubstrates from the occupational exposure.
EU INCO-Copernicus project «Workplace monitoring and occupational health-related studies at some selected phosphate fertilizer plants in Russia, Uzbekistan, Poland, and Romania» (2000-2003)
Collaboration with Univ. “Politehnica” Bucharest (Prof. E. Pincovschi – Project coordinator in Romania) and JINR Dubna (Dr. M. Frontasyeva);
EU Project co-ordinator: Dr. P. Bode, IRI-TU Delft, The Netherlands.
- Decreasing of Ag, As, Au, Co, Fe, K, Ni, Rb, Sb, Sc, Se and Zn concentration;
- Increasing of Rare Earths, Sr and Zr concentration, with a maximum at 10 km;
- Increasing of Ca concentration on East and West directions, with no regular variation on Northeast and Northwest directions.
Modifications of trace elements concentration in four types oftumoral skin tissues were assessed relative to a normal tissue.
VIASAN / R&D program of the Ministry of Education and Research in Romania, during 2001-2004.
Collaboration with "Carol Davila" Medicine and Pharmacy University
Squamous Cell Carcinoma (SCC) – 7
Basal Cell Carcinoma (BCC) - 2
Malignant Melanoma (MM) - 4
Benign tumor: Nevocytic Nevus (NN) tissue -2
Control samples: skin tissue from patients suffering of cutaneous cancer, but from a normal area determined by ahistopathological diagnose - 5 .
Ratios of the elemental concentrations in tumor relative to normal skin tissue (SCC - Squamous Cell Carcinoma, BCC - Basal Cell Carcinoma,MM – Melanoma, NN – Nevocytic Nevus).
Conclusions fertilizer plant
INCT-TL-1 (Tea leaves), INCT-MPH-2 (Mixed Polish herbs), 2002
INCT-CF-3 (Corn Flour), INCT-SB-4 (Soya Bean Flour), 2004 (in progress)
8. Biological materials
E fertilizer plantn scores of the participants for the analysis of the intercomparison sample.