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Publications of Metrology for Chemistry, Health and Environment

Books

G. Basile, E. Ferrara, F. Alasia, P. Pomati, L. D'Amico (editors)
Atti del Convegno Celebrativo di Amedeo Avogadro di Quaregna, 9-11 giugno 2002
A cura dell'Università del Piemonte Orientale e dell'INRIM, 2006.

There has been a large time-delay between the experimental and theoretical scientific achievements of Amedeo Avogadro and their public recognition through the adoption of the chemical unit, the mole, in the international system of units. The importance of his intuitions is noticeable in the bridging function assigned to the Avogadro number, NA, which appears now almost ubiquitously in the equations of chemistry and physics handbooks. Nevertheless, to unfold the intricate way getting to a more clear definition of the Avogadro number, physicists and chemists have still a long work to do. In the June 2002 an international panel of scientist gathered in Oropa (Italy) to let discussion progress as well as to honour the scientific contribution of the great Italian scientist. This volume collects the presentations exposed during the symposium.

International and National Journals

F. A. Zucca, C. Bellei, S. Giannelli, M. R. Terreni, M. Gallorini, E. Rizzio, G. Pezzoli, A. Albertini, L. Zecca
Neuromelanin and iron in human locus coeruleus and substantia nigra during aging: consequences for neuronal vulnerability
Journal of Neural Transmission, Vol. 113, no. 6, pp. 757-67, 2006.

In this study a comparative analysis of iron molecules during aging was performed in locus coeruleus (LC) and substantia nigra (SN), known targets of Parkinson's Disease (PD) and related disorders. LC and SN neurons, especially the SN pars compacta, degenerate in PD and other forms of parkinsonism. Iron and its major molecular forms, such as ferritin and neuromelanin (NM), were measured in LC and SN of normal subjects at various ages. Iron levels were lower, H-ferritin/iron ratio was higher and the iron content in NM was lower in LC than in SN. Iron deposits were abundant in SN tissue, very scarse in LC tissue and completely absent in pigmented neurons of both SN and LC. In both regions H- and L-ferritins were present only in glia. This suggests that in LC neurons iron mobilization and toxicity is lower than that in SN and is efficiently buffered by NM. Ferritins accomplish the same buffering function in glial cells.

L. Zecca, F. A. Zucca, A. Alberini, E. Rizzio, R. G. Fardello
A proposed dual role of neuromelanin in the pathogenesis of Parkinson's disease
Neurology, Vol. 67 (suppl. 2), pp. S8-11, 2006.

In many parkinsonian syndromes, neuromelanin (NM)-containing dopaminergic neurons of the substantia nigra (SN) are selectively targeted by the noxius pathogens. Studies of the constitutional and functional features of human NM allow the formulation of a logical hypothesis on its role in parkinsonian syndromes. In the early stages, NM synthesis and iron-chelating properties may act as a powerful protective mechanism, delaying symptom appearance and/or slowing disease progression. Once these systems have been exhausted, the pathogenic mechanisms affecting cytoplasmic organelles other than NM destroy NM-harboring neurons, with consequent pouring out of NM granules. These in turn activate microglia, causing release of nitric oxide, interleukin-6 and tumor necrosis factor-α, thus becoming an important determinant of disease aggravation. Neuromelanin appears to be a suitable target for devising chemical agents that might modify the course of these diseases.

J. Viallon, P. Moussay, M. Esler, R. Wielgosz, W. Bremser, J. Novák, M. Vokoun, A. Botha, M. Janse Van Rensburg, C. Zellweger, S. Goldthorp, A. Borowiak, F. Lagler, J. Walden, E. Malgeri, M. P. Sassi, P. Morillo Gomez, R. Fernandez Patier, D. Galan Madruga, Jin-Chun Woo, Y. Doo Kim, T. Macé, C. Sutour, A. Surget, B. Niederhauser, D. Schwaller, B. Frigy, I. Györgyné Váraljai, S. Hashimoto, H. Mukai, H. Tanimoto, H. P. Ahleson, A. Egeløv, N. Ladegard, L. Marsteen, K. Tørnkvist, F. R Guenther, J. E Norris, T. L. Hafkenscheid, M. M Van Rijn, P. Quincey, B. Sweeney, S. Langer, B. Magnusson, J. Bastian, V. Stummer, M. Fröhlich, A. Wolf, L. A Konopelko, Y. A. Kustikov, D. V Rumyanstev
International Comparison CCQM-P28: Ozone at ambient level
Metrologia, Vol. 43, no 1A, 08010 (Technical Supplement 2006).

We report a pilot study organized within the Consultative Committee for Amount of Substance (CCQM), in which the ozone reference standards of 23 institutes have been compared to one common reference, the BIPM ozone reference standard, in a series of bilateral comparisons carried out between July 2003 and February 2005. The BIPM, which maintains as its reference standard a standard reference photometer (SRP) developed by the National Institute of Standards and Technology (NIST, United States), served as pilot laboratory. A total of 25 instruments were compared to the common reference standard, either directly (16 comparisons) or via a transfer standard (9 comparisons). The comparisons were made over the ozone mole fraction range 0 nmol/mol to 500 nmol/mol. Two reference methods for measuring ozone mole fractions in synthetic air were compared, thanks to the participation of two institutes maintaining a gas-phase titration system with traceability of measurements to primary gas standards of NO and NO2, while the 23 other instruments were based on UV absorption. In the first instance, each comparison was characterized by the two parameters of a linear equation, as well as their related uncertainties, computed with generalized least-squares regression software. Analysis of these results using the Birge ratio indicated an underestimation of the uncertainties associated with the measurement results of some of the ozone standards, particularly the NIST SRPs. As a final result of the pilot study, the difference from the reference value (BIPM-SRP27 measurement result) and its related uncertainty were calculated for each ozone standard at the two nominal ozone mole fractions of 80 nmol/mol and 420 nmol/mol.

P. Fisicaro, F. Durbiano, F. Giuffredi
Laboratory accreditation in Italy for reference solution production of sucrose in water
Accreditation and Quality Assurance, Vol. 11, no. 7, pp. 336-342, 2006.

The accreditation of Chemifarm srl laboratory for the calibration of two characteristics on the same aqueous solution has been achieved. The process has been executed by the Italian accreditation body for calibration laboratories (SIT). This is the first example of a producer of certified reference solutions in Italy. The solutions are mixtures of sucrose in water at several concentrations and are characterised for refractive index in the range of 1.33299 to 1.38115 and for mass fraction of sucrose in the range of 0 to 30 (commercially expressed in Brix degrees). Both traceability paths, obtained through refractometric and gravimetric methods, are reported. Furthermore, the paper describes the approach adopted to match the criteria based on ISO Guide 34 and ILAC-G 12, the documents with requirements for certified reference material producers, in compliance with those of ISO/IEC 17025, the norm for the laboratory accreditation.

E. Ferrara
TAV: tecnicamente nulla è impossibile
Lo Straniero, n. 68, febbraio 2006.

This note rapidly surveys the technical, environmental, social and health-care related threats posed by the construction of the high-velocity (TAV) Lyon-Turin rail line, including a 57 km long tunnel, across the Alps. 16 billions cubic meters of debris are expected to be extracted out of the mountains, some of them probably containing small amounts of dangerous substances, like asbestos and Uranium minerals. The economics benefits of the project are dubiously defined and distributed, but the endangerment of the population and the territory surrounding it are certain. "Technically, nothing is impossible", sentenced in 2003 the Italian Minister of Infrastructures and Transport. Unfortunately he was the same who, in 2001, transformed by law into normal soils the contaminated wastes extracted from the Firenze-Bologna TAV works, which are now put on trial.

Conference Proceedings

M. Sega, E. Amico di Meane
Determination of PCBs in organic solution: an example of traceability chain
Proceedings of the International Workshop IUPAC-APAT "Combining and reporting analytical results. The role of (metrological) traceability and (measurement) uncertainty for comparing analytical results", Rome (Italy), March 2006.

Polychlorinated biphenyls (PCBs) are extremely persistent and widespread environmental pollutants. Because of their potential health impacts on a wide variety of biota, including human beings, they belong to the twelve classes of Persistent Organic Pollutants (POPs) selected by United Nations Environment Programme (UNEP) under the Stockholm Convention on POPs in 1997. For this reason, the European Community requires the development of measurement methods and standards in order to obtain comparable, consistent, reliable and high quality results for the measurements of these kinds of compounds. The present work deals with the establishment of a traceability chain for the analysis of various PCBs congeners in organic solutions. Traceability is the property of the result of a measurement or the value of a standard whereby it can be related to stated references, usually national or international standards, through an unbroken chain of comparison all having stated uncertainties. The unbroken chain of comparisons is called traceability chain. A correct traceability chain needs to be established in order to obtain high quality reliable results and to compare results of measurements carried out in different places and by different laboratories. Traceable PCBs standards in iso-octane were prepared by accurate weighings from certified reference materials; an uncertainty budget was made, which took into account all the possible uncertainty sources, as the uncertainty of the reference materials and the uncertainty in the mass measurements. Various PCBs congeners were determined via gas-chromatography coupled with mass-spectrometry. The identification of the PCBs congeners in different organic solutions was made by means of the interpretation of the mass spectra obtained in the scan mode. The gas chromatograph coupled with an ion trap mass spectrometer was calibrated using the traceable standards prepared by weighing. The PCBs congeners amount was determined comparing the ion current of proper mass chromatograms of specific fragment ions, selected on the basis of the mass spectra of each congener.

P. Fisicaro, E. Ferrara, E. Prenesti, S. Berto
Quality control of pH measurements through comparison of primary and secondary apparatuses
Proceedings of the International Workshop IUPAC-APAT, (poster session), 2006.

To harmonise results of different methods of pH measurement, primary measurements (Harned cell) of the pH of a phosphate buffer have been considered and the results have been compared with secondary (glass electrode) measurements, executed according to either activity (paH) or concentration (pcH) scales. The aim was to perform a careful inspection of all those parameters significantly affecting the overall uncertainty on both paH and pcH. Uncertainty budgets have been evaluated considering both primary and secondary apparatuses and also including in the study the management of experimental and theoretical aspects of pH in concentration scale.

M. P. Sassi
Traceability of air quality measurements (ozone Italian experience)
Proceedings of the International Workshop IUPAC-APAT, to be published on Royal Society of Chemistry (RCS), (invited paper), 2006.

M. P. Sassi, E. Malgeri, G. Castrofino, S. Curci
Ozone at ambient level: primary standard and traceability chain in Italy
Proceedings of the CAMET International Conference on Metrology, Casablanca (Marocco), (oral session), April 2006.

Technical Reports

F. Alasia, E. Amico di Meane, M. Sega
Ulteriori sviluppi della stazione di preparazione di miscele gassose per via gravimetrica presso l'I.N.RI.M.
Rapporto Tecnico INRIM n. 4, gennaio 2006.

Presso l' I.N.RI.M. - Sezione Massa è stato progettato e realizzato un sistema per la preparazione, mediante il metodo gravimetrico, di miscele gassose campione primarie dato che la realizzazione di tali miscele rappresenta un obiettivo importante per l'Istituto. Nel presente lavoro sono descritte le caratteristiche della stazione per il riempimento e lo svuotamento di bombole le cui parti principali sono due linee di distribuzione per il gas, un sistema per il vuoto e una bilancia per la pesata preliminare delle bombole. Vi è inoltre un comparatore di massa per la pesata di precisione corredato di uno scambiatore meccanico per la movimentazione automatica delle bombole. Sono quindi riportati gli sviluppi che sono stati compiuti su tale strumentazione e che riguardano principalmente il sistema inerente la pesata di precisione, e i risultati delle prove più significative che sono state effettuate per ottimizzare e caratterizzare il sistema stesso.

E. Amico di Meane, M. Sega
EUROMET Project 883 "Vehicle emission comparison" - I.N.RI.M. results
INRIM Technical Report no. 18, July 2006.

This technical report has the aim of presenting the results obtained by the I.N.RI.M. group "Analysis of gases" in the framework of the EUROMET Project 883, on the determination of the concentration of carbon monoxide, carbon dioxide, propane, oxygen in a matrix of nitrogen. In particular, the comparison concerned the determination of the concentrations of carbon monoxide and carbon dioxide by non dispersive infrared spectroscopy (NDIR) and propane by gas chromatography in a mixture with the above components that had been gravimetrically prepared and distributed by the pilot laboratory, namely CEM (Spain). The following results were already been submitted to the pilot laboratory and were included in the evaluation report that is in a draft form.

E. Amico di Meane, M. Sega, F. Rolle
International comparison CCQM-K52 Carbon dioxide in Synthetic air - I.N.RI.M. results
INRIM Technical Report no. 32, October 2006.

This technical report has the aim of presenting the results obtained by the I.N.RI.M. group "Analysis of gases" in the framework of the Key Comparison CCQM-K52, on the determination of the concentration of carbon dioxide at ambient level in a matrix of synthetic air. The comparison concerned the analysis of carbon dioxide by non dispersive infrared spectroscopy (NDIR) in a gaseous mixture that had been gravimetrically prepared and distributed by the coordinating laboratory, namely the Nederlands Meetinstituut Van Swinden Laboratorium (NMi-VSL, the Netherlands). The following results had already been submitted to the coordinating laboratory and were included in the evaluation report that is in a draft form. For I.N.RI.M. this is the first international comparison in which the primary reference gas mixtures used for the NDIR analyser calibration had been gravimetrically realized at I.N.RI.M. by the personnel of the "Analysis of gases" group.

F. Rolle, E. Amico di Meane, M. Sega
Realizzazione di miscele gassose primarie di CO2 in aria sintetica per via gravimetrica presso l'INRIM
Rapporto Tecnico INRIM n. 39, novembre 2006.

Per la partecipazione al confronto chiave CCQM - K52 "Carbon dioxide in synthetic air", sono state realizzate presso l'INRIM quattro miscele gassose primarie di CO2 in aria sintetica, mediante il metodo gravimetrico, alle concentrazioni nominali comprese tra 330 e 390 µmol/mol. Per la prima volta all'INRIM, la composizione delle miscele gassose e le relative incertezze sono state dichiarate sulla base dei dati di pesata ottenuti mediante un comparatore di massa, che consente di effettuare le pesate di precisione delle bombole vuote e dopo ogni fase di riempimento. La loro concentrazione è stata inoltre verificata mediante fotometria infrarossa non dispersiva (NDIR) e le concentrazioni ottenute si sono dimostrate compatibili con i valori gravimetrici, pur evidenziando la presenza di un effetto sistematico, che è attualmente oggetto di indagine. Le concentrazioni gravimetriche e analitiche ottenute per le suddette miscele sono in linea con le concentrazioni nominali attese e i valori dell'incertezza gravimetrica risultano anch'essi assai soddisfacenti.

P. Fisicaro, A. Adriaens, E. Ferrara, E. Prenesti
Amperometric determination of dissolved oxygen
INRIM Technical Report no. 44, December 2006.

This technical report illustrates the results obtained in the development of an electrochemical apparatus for the determination of the amount of dissolved oxygen in aqueous solutions. The project is conducted in cooperation with the Analytical Department of the University of Gent and the Analytical Department of the University of Torino. The measurement system consists in an amperometric cell designed on the model of Clark-type sensors and represents the first attempt at the development of a potential primary standard. The paper describes in detail the principles of the analytical technique as well as the procedure for the setting-up and the calibration of the cell. A preliminary discussion of the main contributions to the overall measurement uncertainty is also reported.