Cultural heritage represents a bridge between the contemporary society and the past populations, ... more Cultural heritage represents a bridge between the contemporary society and the past populations, and a strong collaboration between archaeologists, art historians and analysts may lead to the decryption of the information hidden in an ancient object. Quantitative elemental compositional data play a key role in solving questions concerning dating, provenance, technology, use and the relationship of ancient cultures with the environment. Nevertheless, the scientific investigation of an artifact should be carried out complying with some important constraints: above all the analyses should be as little destructive as possible and performed directly on the object to preserve its integrity. Laser ablation sampling coupled to inductively coupled plasma-mass spectrometry (LA-ICP-MS) fulfils these requirements exhibiting comparably strong analytical performance in trace element determination. This review intends to show through the applications found in the literature how valuable is the contribution of LA-ICP-MS in the investigation of ancient materials such as obsidian, glass, pottery, human remains, written heritage, metal objects and miscellaneous stone materials. The main issues related to cultural heritage investigation are introduced, followed by a brief description of the features of this technique. An overview of the exploitation of LA-ICP-MS is then presented. Finally, advantages and drawbacks of this technique are critically discussed: the fit for purpose and prospects of the use of LA-ICP-MS are presented.
International Journal of Environmental Analytical Chemistry, 2011
... DOI: 10.1080/03067319.2010.496049 Damiano Monticelli a * , Andrea Pozzi a , Elena Ciceri a &a... more ... DOI: 10.1080/03067319.2010.496049 Damiano Monticelli a * , Andrea Pozzi a , Elena Ciceri a & Barbara Giussani a pages 213-229. Available online: 22 Feb 2011. ...
ABSTRACT Research in voltammetric speciation methods has been mainly driven by the research inter... more ABSTRACT Research in voltammetric speciation methods has been mainly driven by the research interests of the oceanographic scientific community and methods were subsequently adapted to freshwater conditions. Nonetheless, different processes, variability of geological, chemical, biological and ecological settings on the one side, and different human land and water uses on the other imply specific needs and a strong shift in concerns for inland waters in terms of investigated analytes. This review paper focuses on speciation of trace elements in freshwater by voltammetric techniques, giving information on and a critical assessment of the state of the art in this field. Methods determining covalently bound substituents, redox species and element forms differing in the nature of their complexed substituents were considered, according to the IUPAC definition of species. Three relevant topics are discussed: an overview of existing voltammetric speciation methods, with emphasis on practical features; current knowledge in the field of trace element speciation in freshwater bodies, organised by element and matrix; and future perspectives and needs for freshwater speciation studies. As a general outcome, a complete picture of trace element speciation in freshwater matrices is far from being achieved.
Nei giorni 7 – 8 settembre 2001 è stata effettuata una campagna di campionamento di ghiaccio, nev... more Nei giorni 7 – 8 settembre 2001 è stata effettuata una campagna di campionamento di ghiaccio, neve ed acqua superficiale sul ghiacciaio della Marmolada (Dolomiti occidentali) che ha interessato sia la zona di accumulo delle precipitazioni nevose sia quella di ablazione del ghiac-ciaio alle fronti occidentale, centrale ed orientale. Le analisi chimiche, effettuate sia direttamente sul ghiacciaio mediante strumentazione elettroanalitica portatile sia in laboratorio, hanno messo in evidenza le interazioni chimiche che avvengono tra le acque di fusione del ghiaccio e le rocce carbonatiche del bacino, e gli effetti dell'elevato impatto antropico legato all'attività sportiva praticata sul ghiacciaio sia d'inverno sia d'estate. MARM OLADA 44 45 INTRODUZIONE Assetto geografico e geomorfologico Il Massiccio della Marmolada è ubicato nelle Alpi Dolomitiche, al confine tra le province di Belluno e Trento. La linea spartiacque che lo attraversa rappresenta un tratto del displuvi...
International Journal of Environmental Analytical Chemistry, 2007
... was found with linearity up to 10 µg L-1. In the abandoned mining area of Val Vedello (Orobic... more ... was found with linearity up to 10 µg L-1. In the abandoned mining area of Val Vedello (OrobicAlps, Italy), measured uranium concentrations in water ranged from 0.3 µg L-1 above the uranium mineralization levels to 145 µg L-1 in groundwaters percolating from mine galleries. ...
In the present work we demonstrated that the digestion of difficult matrices (high boiling petroc... more In the present work we demonstrated that the digestion of difficult matrices (high boiling petrochemical fractions and distillation bottoms) can be achieved by oxidation with nitric acid vapours at atmospheric pressure employing simple laboratory glassware. The application of this procedure as a digestion method prior to Total Reflection X-Ray Fluorescence (TXRF) is presented, although the employment of other detection techniques may be foreseen. The method ensured a fast, less than half an hour, treatment time and detection limits in the range 20-100 μg/kg for As, Bi, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, Zn, whereas higher values were obtained for Ba, Ca, K, P, Rh, Ti and V (0.3-3 mg/kg). The potentialities and limitations of this procedure were discussed: the application to a broad range of matrices may be foreseen.
Voltammetric techniques have emerged as powerful methods for the determination and speciation of ... more Voltammetric techniques have emerged as powerful methods for the determination and speciation of trace and ultratrace elements without any preconcentration in several research fields. Nevertheless, large sample volumes are typically required (10 mL), which strongly limits their application and/or the precision of the results. In this work, we report a 20-fold reduction in sample size for trace and ultratrace elemental determination and speciation by conventional voltammetric instrumentation, introducing the lowest amount of sample (0.5 mL) in which ultratrace detection has been performed up to now. This goal was achieved by a careful design of a new sample holder. Reliable, validated results were obtained for the determination of trace/ultratrace elements in rainwater (Cd, Co, Cu, Ni, Pb) and seawater (Cu). Moreover, copper speciation in seawater samples was consistently determined by competitive ligand equilibration-cathodic stripping voltammetry (CLE-CSV). The proposed apparatus showed several advantages: (1) 20-fold reduction in sample volume (the sample size is lowered from 120 to 6 mL for the CLE-CSV procedure); (2) decrease in analysis time due to the reduction in purging time up to 2.5 fold; (3) 20-fold drop in reagent consumption. Moreover, the analytical performances were not affected: similar detection capabilities, precision and accuracy were obtained. Application to sample of limited availability (e.g. porewaters, snow, rainwater, open ocean water, biological samples) and to the description of high resolution temporal trends may be easily foreseen.
A new method based on adsorptive cathodic stripping voltammetry with catalytic enhancement for th... more A new method based on adsorptive cathodic stripping voltammetry with catalytic enhancement for the determination of total dissolved iron in seawater is reported. It was demonstrated that iron detection at the ultratrace level (0.1 nM) may be achieved in small samples (500 μL) with high sensitivity, no need for purging, no added oxidant and a limit of detection of 5 pM. The proposed method is based on the adsorption of the complex Fe/2,3- dihydroxynaphthalene (DHN) exploiting the catalytic effect of atmospheric oxygen. As opposite to the original method (Obata and van den Berg, Anal. Chem. 2001, 73, 2522-2528), atmospheric oxygen dissolved in solution replaced bromate ions in the oxidation of the iron complex: removing bromate reduces the blank level and avoid the use of a carcinogenic species. Moreover, the new method is based on a recently introduced hardware that enables the determinations to be performed in 500 μL samples. The analysis were carried out on buffered samples (pH 8.15, HEPPS 0.01 M), 10 μM DHN and iron quantified by the standard addition method. The sensitivity is 49 nA nM-1 min-1 with 30 s deposition time and the LOD is equal to 5 pM. As a result, the whole procedure for the quantification of iron in one sample requires around 7.5 minutes. The new method was validated via analysis on two reference samples (SAFe S and SAFe D2) with low iron content collected in the North Pacific Ocean.
International Journal of Environmental Analytical Chemistry, 2007
Adsorptive cathodic stripping voltammetry (AdCSV) with HDME and a chloranilic acid ligand was use... more Adsorptive cathodic stripping voltammetry (AdCSV) with HDME and a chloranilic acid ligand was used in the trace analysis of uranyl ions at pH = 2 in low-ionic-strength groundwaters around mining areas. Upon optimization, the limit of detection around 0.10 µg L was found with linearity up to 10 µg L. In the abandoned mining area of Val Vedello (Orobic Alps, Italy), measured uranium concentrations in water
Cultural heritage represents a bridge between the contemporary society and the past populations, ... more Cultural heritage represents a bridge between the contemporary society and the past populations, and a strong collaboration between archaeologists, art historians and analysts may lead to the decryption of the information hidden in an ancient object. Quantitative elemental compositional data play a key role in solving questions concerning dating, provenance, technology, use and the relationship of ancient cultures with the environment. Nevertheless, the scientific investigation of an artifact should be carried out complying with some important constraints: above all the analyses should be as little destructive as possible and performed directly on the object to preserve its integrity. Laser ablation sampling coupled to inductively coupled plasma-mass spectrometry (LA-ICP-MS) fulfils these requirements exhibiting comparably strong analytical performance in trace element determination. This review intends to show through the applications found in the literature how valuable is the contribution of LA-ICP-MS in the investigation of ancient materials such as obsidian, glass, pottery, human remains, written heritage, metal objects and miscellaneous stone materials. The main issues related to cultural heritage investigation are introduced, followed by a brief description of the features of this technique. An overview of the exploitation of LA-ICP-MS is then presented. Finally, advantages and drawbacks of this technique are critically discussed: the fit for purpose and prospects of the use of LA-ICP-MS are presented.
International Journal of Environmental Analytical Chemistry, 2011
... DOI: 10.1080/03067319.2010.496049 Damiano Monticelli a * , Andrea Pozzi a , Elena Ciceri a &a... more ... DOI: 10.1080/03067319.2010.496049 Damiano Monticelli a * , Andrea Pozzi a , Elena Ciceri a & Barbara Giussani a pages 213-229. Available online: 22 Feb 2011. ...
ABSTRACT Research in voltammetric speciation methods has been mainly driven by the research inter... more ABSTRACT Research in voltammetric speciation methods has been mainly driven by the research interests of the oceanographic scientific community and methods were subsequently adapted to freshwater conditions. Nonetheless, different processes, variability of geological, chemical, biological and ecological settings on the one side, and different human land and water uses on the other imply specific needs and a strong shift in concerns for inland waters in terms of investigated analytes. This review paper focuses on speciation of trace elements in freshwater by voltammetric techniques, giving information on and a critical assessment of the state of the art in this field. Methods determining covalently bound substituents, redox species and element forms differing in the nature of their complexed substituents were considered, according to the IUPAC definition of species. Three relevant topics are discussed: an overview of existing voltammetric speciation methods, with emphasis on practical features; current knowledge in the field of trace element speciation in freshwater bodies, organised by element and matrix; and future perspectives and needs for freshwater speciation studies. As a general outcome, a complete picture of trace element speciation in freshwater matrices is far from being achieved.
Nei giorni 7 – 8 settembre 2001 è stata effettuata una campagna di campionamento di ghiaccio, nev... more Nei giorni 7 – 8 settembre 2001 è stata effettuata una campagna di campionamento di ghiaccio, neve ed acqua superficiale sul ghiacciaio della Marmolada (Dolomiti occidentali) che ha interessato sia la zona di accumulo delle precipitazioni nevose sia quella di ablazione del ghiac-ciaio alle fronti occidentale, centrale ed orientale. Le analisi chimiche, effettuate sia direttamente sul ghiacciaio mediante strumentazione elettroanalitica portatile sia in laboratorio, hanno messo in evidenza le interazioni chimiche che avvengono tra le acque di fusione del ghiaccio e le rocce carbonatiche del bacino, e gli effetti dell'elevato impatto antropico legato all'attività sportiva praticata sul ghiacciaio sia d'inverno sia d'estate. MARM OLADA 44 45 INTRODUZIONE Assetto geografico e geomorfologico Il Massiccio della Marmolada è ubicato nelle Alpi Dolomitiche, al confine tra le province di Belluno e Trento. La linea spartiacque che lo attraversa rappresenta un tratto del displuvi...
International Journal of Environmental Analytical Chemistry, 2007
... was found with linearity up to 10 µg L-1. In the abandoned mining area of Val Vedello (Orobic... more ... was found with linearity up to 10 µg L-1. In the abandoned mining area of Val Vedello (OrobicAlps, Italy), measured uranium concentrations in water ranged from 0.3 µg L-1 above the uranium mineralization levels to 145 µg L-1 in groundwaters percolating from mine galleries. ...
In the present work we demonstrated that the digestion of difficult matrices (high boiling petroc... more In the present work we demonstrated that the digestion of difficult matrices (high boiling petrochemical fractions and distillation bottoms) can be achieved by oxidation with nitric acid vapours at atmospheric pressure employing simple laboratory glassware. The application of this procedure as a digestion method prior to Total Reflection X-Ray Fluorescence (TXRF) is presented, although the employment of other detection techniques may be foreseen. The method ensured a fast, less than half an hour, treatment time and detection limits in the range 20-100 μg/kg for As, Bi, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, Zn, whereas higher values were obtained for Ba, Ca, K, P, Rh, Ti and V (0.3-3 mg/kg). The potentialities and limitations of this procedure were discussed: the application to a broad range of matrices may be foreseen.
Voltammetric techniques have emerged as powerful methods for the determination and speciation of ... more Voltammetric techniques have emerged as powerful methods for the determination and speciation of trace and ultratrace elements without any preconcentration in several research fields. Nevertheless, large sample volumes are typically required (10 mL), which strongly limits their application and/or the precision of the results. In this work, we report a 20-fold reduction in sample size for trace and ultratrace elemental determination and speciation by conventional voltammetric instrumentation, introducing the lowest amount of sample (0.5 mL) in which ultratrace detection has been performed up to now. This goal was achieved by a careful design of a new sample holder. Reliable, validated results were obtained for the determination of trace/ultratrace elements in rainwater (Cd, Co, Cu, Ni, Pb) and seawater (Cu). Moreover, copper speciation in seawater samples was consistently determined by competitive ligand equilibration-cathodic stripping voltammetry (CLE-CSV). The proposed apparatus showed several advantages: (1) 20-fold reduction in sample volume (the sample size is lowered from 120 to 6 mL for the CLE-CSV procedure); (2) decrease in analysis time due to the reduction in purging time up to 2.5 fold; (3) 20-fold drop in reagent consumption. Moreover, the analytical performances were not affected: similar detection capabilities, precision and accuracy were obtained. Application to sample of limited availability (e.g. porewaters, snow, rainwater, open ocean water, biological samples) and to the description of high resolution temporal trends may be easily foreseen.
A new method based on adsorptive cathodic stripping voltammetry with catalytic enhancement for th... more A new method based on adsorptive cathodic stripping voltammetry with catalytic enhancement for the determination of total dissolved iron in seawater is reported. It was demonstrated that iron detection at the ultratrace level (0.1 nM) may be achieved in small samples (500 μL) with high sensitivity, no need for purging, no added oxidant and a limit of detection of 5 pM. The proposed method is based on the adsorption of the complex Fe/2,3- dihydroxynaphthalene (DHN) exploiting the catalytic effect of atmospheric oxygen. As opposite to the original method (Obata and van den Berg, Anal. Chem. 2001, 73, 2522-2528), atmospheric oxygen dissolved in solution replaced bromate ions in the oxidation of the iron complex: removing bromate reduces the blank level and avoid the use of a carcinogenic species. Moreover, the new method is based on a recently introduced hardware that enables the determinations to be performed in 500 μL samples. The analysis were carried out on buffered samples (pH 8.15, HEPPS 0.01 M), 10 μM DHN and iron quantified by the standard addition method. The sensitivity is 49 nA nM-1 min-1 with 30 s deposition time and the LOD is equal to 5 pM. As a result, the whole procedure for the quantification of iron in one sample requires around 7.5 minutes. The new method was validated via analysis on two reference samples (SAFe S and SAFe D2) with low iron content collected in the North Pacific Ocean.
International Journal of Environmental Analytical Chemistry, 2007
Adsorptive cathodic stripping voltammetry (AdCSV) with HDME and a chloranilic acid ligand was use... more Adsorptive cathodic stripping voltammetry (AdCSV) with HDME and a chloranilic acid ligand was used in the trace analysis of uranyl ions at pH = 2 in low-ionic-strength groundwaters around mining areas. Upon optimization, the limit of detection around 0.10 µg L was found with linearity up to 10 µg L. In the abandoned mining area of Val Vedello (Orobic Alps, Italy), measured uranium concentrations in water
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