Arsenic in hair by INAA — A major recent murder case

In the fall of 1990, Blanche Kiser Moore was tried in the state of North Carolina for the murder, by arsenic poisoning, of a former boyfriend of hers (RCR), found guilty of first-degree murder by the jury, and sentenced to death. Instrumental neutron activation analysis (INAA), with gamma-ray spectrometry, was carried out on sectioned hair samples from, six possible poisoning victims of hers, by the authors, and the results presented at the trial by VPG. Details, of the sample preparations, the numerical results obtained, and their interpretation are presented. Also presented are difficulties involved in such analysis, and discussion of the fast-neutron interferences caused by Se and Br.     

210Pb fluxes in sediment layers sampled from Northern Patagonia lakes

Unsupported ²¹⁰Pb fluxes were determined from sediment core inventories in lakes located in Northern Patagonia, Argentina. Total ²¹⁰Pb, ²²⁶Ra, associated with supported ²¹⁰Pb, and ¹³⁷Cs specific activity profiles were measured by gamma-ray spectrometry. Unsupported ²¹⁰Pb fluxes showed very low values when compared to other regions, with a 12 fold variation, ranging from 4 to 48 Bq m^–2.y^–1. The linear correlation observed between the ²¹⁰Pb fluxes and¹³⁷Cs cumulative fluxes in sediment cores sampled from water bodies within a zone with similar precipitation demonstrated that both radioisotopes behave in the same manner in these systems concerning the processes occurred from fallout to sediment deposition, and that there are no appreciable local or regional sources of unsupported ²¹⁰Pb. Positive correlation of ²¹⁰Pb fluxes with organic matter contents of the uppermost sediment core layers was also observed.     

Chemical characterization of Bronze Age pottery from Greek South Aegean islands by INAA

This paper presents the results on 20 minor and trace elements of a wide analytical programme — based on neutron activation and statistical analysis — which deals with the chemical characterization of pottery from the Cycladic islands and Crete, during the Bronze Age (Cycladic period), with particular reference to Akrotiri on Thera. Multivariate analysis of the neutron activation data showed that the majority of the pottery found in Akrotiri was locally made, by one type of clay. This in connection with the local style that Akrotiri had introduced, supports the idea of an autonomous development. Contacts with neighbouring islands were also confirmed.     

Trace elements content in size-classified volcanic ashes as determined by inductively coupled plasma-mass spectrometry

At present there is an increasing concern as regards the release of potentially toxic metals into the environment. Volcanic eruptions are a natural source of metals and metalloids in the atmosphere. Toxic trace elements ejected during an eruptive episode may produce hazardous effects for people and the environment in areas close to the volcano. In this context, a study was undertaken to investigate the concentration of metal and metalloids in ashes ejected from Copahue volcano, Neuquén, Argentina. Two samples (A and B) of deposited particles were collected one day after the first eruption and size-fractionated in four sub-samples (S1, S2, S3 and S4). Analysis was performed by inductively coupled plasma-mass spectrometry (ICP-MS) and the accuracy for the entire analytical procedure was performed by means of the certified reference material CRM GBW 07105 Rocks (NRCCRM, China). The elements considered were: As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, U, V and Zn. The adverse effect of potentially interfering species on the mass-spectrometric determination of these elements was also taken into account. The concentration intervals found in the four fractions are as follows (in μg g⁻¹): As, 6.0-2.6; Cd, 0.71-0.36; Cr, 29.5-54.0; Cu, 132-49.0; Hg, 0.020-0.007; Ni, 36.0-26.0; Pb, 15.5-2.55; Sb, 1.07-0.30; U, 2.57-1.94; V, 152-106; Zn, 85.5-55.0. The elements with the highest concentrations were: Cu, V and Zn. All fractions, in both samples, were found to be enriched in some toxic trace elements in the following order Sb>Cd>As. On the contrary, samples were depleted in Ni, Cr and Hg. Lead was the element that exhibits a noticeable difference in concentration between the finer and coarser fractions.     

Heavy metal inputs in Northern Patagonia lakes from short sediment core analysis

Summary Heavy metal profiles of short sediment cores sampled from lakes located in Nahuel Huapi National Park, Northern Patagonia, Argentina, were determined by INAA. Core dating was performed by measuring natural ²¹⁰Pb and anthropogenic ¹³⁷Cs, and by identification of tephra layers. No evidence was found for the input increase of the trace elements Sb, Ba, Cs, Zn, Co, Hf, Ni, Se, Sr, Ti, U, and V in the lake environment. High As concentrations (up to 250 μg ^. g^-1) were found in relation with the diffusion processes of Mn and Fe oxides. Strong correlation was observed between the Br concentration and organic matter content, but no evidence was found for the relevant increase of Br inputs in recent years. Ag concentrations were found to be enriched in the upper core layers over the baseline values determined for deep layers ranging from 0.1 to 0.2 μg ^. g^-1. Hg concentration profiles were also enriched in the upper core layers over the baseline (from less than 0.07 to 0.2 μg ^. g^-1 for pre-industrial time, to 0.1 to 0.3 μg ^. g^-1 for modern times) but in relation with the increased organic matter content of the sediment.     

Application of INAA to reveal the chemical evolution of selected volcanic eruptiva from Santorini, Greece

The pumiceous products of the large-scale explosive eruptions at Santorini show a high grade of similarity in their optical appearance as well as in their chemical composition. The demand for a clear classification of these eruption products was raised from archaeological research, where pumice can be interpreted as a “post-eruption” time marker. The aim of this work was to find elements that underwent significant changes because of geochemical processes and that could be indicative for a distinction of pumice produced by the five major explosive eruptions. INAA of 25 elements allows a clear classification and contributes new information to the chemical evolution of Santorini volcano. This revised version was published online in July 2006 with corrections to the Cover Date.     

Physico-chemical characterization of crystalline phases in fly ashes

Fuel oil combustion in power plants, domestic heating systems and diesel engines, causes the emission in the environment of particles with a typical structure and composition: the cenospheres.These particles are produced during the microdrop fuel oil combustion, when air and fuel are injected into the combustion chamber; they have a spheroidal morphology and a spongy structure.Cenospheres are constituted by an amorphous component rich in C, S, Si, Fe and Al; phases composed by microcrystals of sulphates, oxides and pure metallic elements or their alloys, are frequently present in the cenospheres.These crystalline phases are important from environmental and toxicological points of view both because they are composed of heavy metals, and because they can play an important role in heterogeneous catalysis.We started to study these crystalline phases by analytical electron microscopy techniques and electron energy loss spectrometry to define and characterise their structure and composition.     

Elemental characterization of TSP and two size fractions of airborne particulate matter from Tehran by INAA and AAS

Airborne particulate matter has been collected by a high volume and a Gent-type stacked filter unit (SFU) low volume sampler during the 2000-2001 period. The high volume sampler used S&S cellulosic and the SFU two Nuclepore polycarbonate filters to collect fine and coarse size fractions. The elemental analysis of the collected TSP, fine and coarse particles has been performed using instrumental neutron activation analysis and atomic absorption spectrometry. Twenty-two trace elements on Nuclepore and twenty-four elements on S&S filters have been measured. The collected data have been compared with the previous data of Tehran air and with other cities in the world. This revised version was published online in July 2006 with corrections to the Cover Date.     

Elemental characterization of impurities at trace and ultra-trace levels in metallurgical lead samples by INAA

The purity of several economically important metals is routinely verified by a reference material. Further, it is essential to provide a means of maintaining the consistency between laboratories and on disseminating the accurate value.This work, developed within an activity of certification promoted by EURATOM, reports the results on impurity determination (Ag, As, Cd, Ni, Sb, Sn, Te and Zn) at trace (µg g^{− 1}) and ultra-trace (ng g^{− 1}) levels in three metallurgical lead samples (99.99% of purity). Among the different analytical techniques available for the characterization, the use of a nuclear technique, i.e. Instrumental Nuclear Activation Analysis, has allowed to reach high sensitivity and to obtain accurate values for these elements.The irradiations were performed in the rotating rack (Lazy Susan) and in the central channel of the Triga Mark II reactor reaching a total integrated flux of 9.36 × 10¹⁷ n cm^{− 2} and 2 × 10¹⁹ n cm^{− 2}, respectively.The results about the determination of elements such as Ni, Sn, Te and Zn present at ultra-trace levels (ng/g), are showed and discussed. This task is very interesting for the radio-analytical and methodological implications: in fact, for analyzing them a radiochemical separation is involved and an anti-Compton gamma spectrometer is necessary due to their very low levels.     

INAA for the characterization of airborne particulate matter from the industrial area of Islamabad city

Air particulate matter (PM) was collected in two size fractions using stacked filter units (SFUs) provided by the International Atomic Energy Agency (IAEA) from the industrial area of Islamabad. Nucleopore polycarbonate filters were used for collecting from Oct 98 to Jun 99 the particulate matter in coarse and fine size fractions. The samples were characterized by the instrumental neutron activation analysis (INAA). About 33 elements were quantified using different irradiation and counting protocols.     

INAA and PIXE characterization of heavy metals and rare earth elements emissions from phosphorite handling in harbours

Harbour activities such as loading, unloading and transport of materials may be an important source of Atmospheric Particulate Matter (APM). Depending on the materials, the type of operation and the meteorological conditions, these activities may have an impact on the levels of APM around harbour areas. The aim of this work was to characterize the emissions of dust providing from operations associated with phosphorite handling in harbours. Phosphorite is a non-detrital sedimentary rock which contains high amounts of phosphate bearing minerals and is used for the production of phosphorous based fertilizers. When handled in harbours frequently cause visual and environment impacts due to its physical and chemical characteristics. The techniques Instrumental Neutron Activation Analysis and Particle Induced X-ray Emission were applied as sensitive analytical tools for the determination of heavy metals and rare earth elements in phosphorite and in the APM sampled in the harbour during the unloading operations. Results showed that manipulation of phosphorite during harbour operations resulted in high emissions of particles, principally from the coarse fraction. These emissions were enriched in rare earth elements and heavy metals and were very affected by the provenience of the phosphorite.     

Determination of phosphorus in polymers by INAA

An INAA technique employing beta spectrometry was developed for the determination of phosphorus in polymers. The (n,γ) reaction on phosphorus produces³²P, half-life 14.3 days, a pure beta emitter with end-point energy 1.71 MeV. Polymer samples in the form of powders, films and pellets are irradiated and then counted with a plastic scintillator. The beta spectrum is corrected for interferences (especially Sb, Zn and Br which are quantified by gamma spectrometry) and for energy loss in the thick sample. Samples must also be analyzed for S and Cl which cause nuclear interferences. With an irradiation time of 4 hours at a neutron flux of 5·10¹¹ n·cm^{−2 s −1}, decay time 10 days and counting time 10 minutes, the sensitivity is 520 counts/μg phosphorus and the detection limit is typically 2μg/g.     

Trace element characterization of medieval and post-medieval glass objects by means of INAA and EPMA

Instrumental neutron activation analysis (INAA) was applied to create a database for minor and trace elements in medieval and post-medieval glassware in order to establish a methodology for estimating the origin of the glass objects. First, general characterization of glass types was done on the basis of the results obtained by the use of electron probe microanalysis (EPMA). Information received by the use of INAA provided the additional valuable data reflecting to some extent the method of preparation or the differentiation of various sources of certain raw materials. Several glass samples and a set of various reference glass materials were used for our experiments.     

Elution behaviour and environmental impact of heavy metals and rare-earth elements from volcanic ashes of Mt. Oyama,Miyake Island

To obtain information on the environmental impact of materials eluted from volcanic ashes of Mt. Oyama, Miyake Island, which erupted in July 2000, the dissolution behaviours of heavy metals and rare-earth elements from the volcanic ashes were examined. The most important characteristic of the Mt. Oyama eruption is that sulphur dioxide (SO₂) gas has been continuously released, and all persons living on Miyake Island have been required to evacuate. To estimate in terms of the volcanic eruption using SO₂ gas, the ash nature in Mt. Usu, Hokkaido, was also examined and compared with that in Mt. Oyama. When rain water mixed the ashes, the water from the ashes of Mt. Oyama became acidic because of the sulphuric acid. Therefore, SO₂ gas in Mt. Oyama can accelerate the dissolution of protons and heavy metals in the ashes, whereas the rain water in Mt. Usu was not acidic and the dissolution of the heavy metals was not so evident compared with that in the case of Mt. Oyama. With this sulphuric acid, heavy metals such as As, Cd, Pb and Hg in the ashes in Mt. Oyama easily dissolved owing to the low pH. The ashes in Mt. Oyama had been released for eight years and the amount of fallen ashes was estimated to be 33 billion tons. The weights of the harmful heavy metals in the volcanic ashes, such as As, Cd, Pb and Hg, were estimated to be 3.8?×?10², 1.3?×?10³, 1.1?×?10³ and 29?kg, respectively, and these heavy metals were dissolved and diluted in seawater. Therefore, the concentration and species (chemical form) of these metals should be carefully monitored in the future. Moreover, SO₂ gas, which has a direct effect on human health and has been monitored continuously, causes other effects, such as facilitation of metal ion elution and rock aeration.     

Trace element characterization by INAA of three sediments to be certified as standard reference materials

Three environmental matrices proposed as Certified Reference Materials, issued by the EU Standards, Measurement and Testing Programme (SMTP) formerly Bureau Communautaire de Reference (BCR) have been characterized for their trace element contents.The materials are: BCR 277 R Estuarine Sediment, BCR 280 R Lake Sediment and BCR 320 R Channel Sediment.Several trace elements, including As, Co, Cr, Fe, Mn, Ni, Sb, Sc, Th, U and Zn have been determined by our laboratory using Instrumental Neutron Activation Analysis (INAA). Our contributed values are being considered for the final certification.     

Identification and characterization of individual airborne volcanic ash particles by Raman microspectroscopy

We present for the first time the Raman microspectroscopic identification and characterization of individual airborne volcanic ash (VA) particles. The particles were collected in April/May 2010 during research aircraft flights, which were performed by Deutsches Zentrum für Luft- und Raumfahrt in the airspace near the Eyjafjallajökull volcano eruption and over Europe (between Iceland and Southern Germany). In addition, aerosol particles were sampled by an Electrical Low Pressure Impactor in Munich, Germany. As references for the Raman analysis, we used the spectra of VA collected at the ground near the place of eruption, of mineral basaltic rock, and of different minerals from a database. We found significant differences in the spectra of VA and other aerosol particles (e.g., soot, nitrates, sulfates, and clay minerals), which allowed us to identify VA among other atmospheric particulate matter. Furthermore, while the airborne VA shows a characteristic Raman pattern (with broad band from ca. 200 to ca. 700 cm^?1 typical for SiO₂ glasses and additional bands of ferric minerals), the differences between the spectra of aged and fresh particles were observed, suggesting differences in their chemical composition and/or structure. We also analyzed similarities between Eyjafjallajökull VA particles collected at different sampling sites and compared the particles with a large variety of glassy and crystalline minerals. This was done by applying cluster analysis, in order to get information on the composition and structure of volcanic ash.

Determination of trace elements in honey by INAA in Turkey

Instrumental neutron activation analysis was applied to the determination of As, Cr, Sb, K, Br, Zn, Fe, Co in Turkish honey. Irradiation time was 6 h underwater at a thermal flux of 10¹³ n cm^–2 s^–1; cooling times of 100 h and 3–4 weeks and counting times of 5000 s and 80.000 sec were used. The detection limit for As is 0.01 ppm for honey matrix under these conditions. A technique was developed for sealing the quartz tube containing the honey with flame.     

Variations in atmospheric trace element deposition studied by INAA of peat cores from ombrotrophic bogs

In the present work INAA is used to determine as many elements as possible in peat samples from ombrotrophic bogs. Results for depth distribution profiles of some elements of particular interest are presented for selected bogs from areas with highly different input from long-range atmospheric transport of pollutants. In addition to information on air pollution, the data provide knowledge about contribution from natural processes to the airborne supply of some elements, such as in the case of selenium.