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1.
Proc Natl Acad Sci U S A ; 116(27): 13210-13214, 2019 07 02.
Artigo em Inglês | MEDLINE | ID: mdl-31160460

RESUMO

Art forgeries have existed since antiquity, but with the recent rapidly expanding commercialization of art, the approach to art authentication has demanded increasingly sophisticated detection schemes. So far, the most conclusive criterion in the field of counterfeit detection is the scientific proof of material anachronisms. The establishment of the earliest possible date of realization of a painting, called the terminus post quem, is based on the comparison of materials present in an artwork with information on their earliest date of discovery or production. This approach provides relative age information only and thus may fail in proving a forgery. Radiocarbon (14C) dating is an attractive alternative, as it delivers absolute ages with a definite time frame for the materials used. The method, however, is invasive and in its early days required sampling tens of grams of material. With the advent of accelerator mass spectrometry (AMS) and further development of gas ion sources (GIS), a reduction of sample size down to microgram amounts of carbon became possible, opening the possibility to date individual paint layers in artworks. Here we discuss two microsamples taken from an artwork carrying the date of 1866: a canvas fiber and a paint chip (<200 µg), each delivering a different radiocarbon response. This discrepancy uncovers the specific strategy of the forger: Dating of the organic binder delivers clear evidence of a post-1950 creation on reused canvas. This microscale 14C analysis technique is a powerful method to reveal technically complex forgery cases with hard facts at a minimal sampling impact.

2.
Anal Chem ; 88(17): 8570-6, 2016 09 06.
Artigo em Inglês | MEDLINE | ID: mdl-27396439

RESUMO

A new instrumental setup, combining laser ablation (LA) with accelerator mass spectrometry (AMS), has been investigated for the online radiocarbon ((14)C) analysis of carbonate records. Samples were placed in an in-house designed LA-cell, and CO2 gas was produced by ablation using a 193 nm ArF excimer laser. The (14)C/(12)C abundance ratio of the gas was then analyzed by gas ion source AMS. This configuration allows flexible and time-resolved acquisition of (14)C profiles in contrast to conventional measurements, where only the bulk composition of discrete samples can be obtained. Three different measurement modes, i.e. discrete layer analysis, survey scans, and precision scans, were investigated and compared using a stalagmite sample and, subsequently, applied to terrestrial and marine carbonates. Depending on the measurement mode, a precision of typically 1-5% combined with a spatial resolution of 100 µm can be obtained. Prominent (14)C features, such as the atomic bomb (14)C peak, can be resolved by scanning several cm of a sample within 1 h. Stalagmite, deep-sea coral, and mollusk shell samples yielded comparable signal intensities, which again were comparable to those of conventional gas measurements. The novel LA-AMS setup allowed rapid scans on a variety of sample materials with high spatial resolution.

3.
Sci Total Environ ; 738: 139700, 2020 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-32534284

RESUMO

Radiocarbon (14C) is broadly used in oceanography to determine water ages, trace water circulation, and develop sediment- and sclerochronologies. These applications require an accurate knowledge of marine 14C levels, which have been largely perturbed by human activities. Globally during the last century the above-ground nuclear weapon testings have been the primary cause of the increased atmospheric and marine 14C. However, other anthropogenic sources may have caused important regional deviations from the bomb pulse. For the last 70 years European nuclear fuel reprocessing plants have been major contributors of 14C to air and oceans, yet, their regional impact on surrounding marine 14C has been largely overlooked. Here we use a collection of bivalve shells of known capture date and age collected from various locations, including the North Sea, the Irish Sea, Norway, and the Bay of Biscay to reconstruct the sea surface 14C over the last five decades. The measured 14C values for the period 1969-2019, reported in fraction modern, ranged from 1.1 to 1.6 in coastal waters of the Netherlands and from 1.2 to 3.2 along the coast of the UK, indicating significantly higher levels of 14C than those expected for the marine bomb pulse (0.950-1.150). The 14C peaks revealed by the shells coincide with the increase of liquid 14C releases reported from the reprocessing plants of La Hague into the English Channel, and from Sellafield into the Irish Sea. Conversely, the shells from Norway and Spain showed 14C values close to the range of the global marine bomb pulse. The observed large spatial and temporal differences in sea surface 14C show that 14C dating and tracing studies could become problematic in the English Channel, Irish Sea and North Sea for the time period covering the discharge of liquid 14C from the reprocessing plants.

4.
Bioanalysis ; 10(5): 321-339, 2018 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-29451392

RESUMO

AIM: Although regulatory guidances require human metabolism information of drug candidates early in the development process, the human mass balance study (or hADME study), is performed relatively late. hADME studies typically involve the administration of a 14C-radiolabelled drug where biological samples are measured by conventional scintillation counting analysis. Another approach is the administration of therapeutic doses containing a 14C-microtracer followed by accelerator mass spectrometry (AMS) analysis, enabling hADME studies completion much earlier. Consequently, there is an opportunity to change the current drug development paradigm. MATERIALS & METHODS: To evaluate the applicability of the MICADAS-cAMS method, we successfully performed: the validation of MICADAS-cAMS for radioactivity quantification in biomatrices and, a rat ADME study, where the conventional methodology was assessed against a microtracer MICADAS-cAMS approach. RESULTS & DISCUSSION: Combustion AMS (cAMS) technology is applicable to microtracer studies. A favorable opinion from EMA to complete the hADME in a Phase I setting was received, opening the possibilities to change drug development.


Assuntos
Radioisótopos de Carbono/sangue , Radioisótopos de Carbono/farmacocinética , Radioisótopos de Carbono/urina , Piridinas/sangue , Piridinas/farmacocinética , Piridinas/urina , Pirimidinas/sangue , Pirimidinas/farmacocinética , Pirimidinas/urina , Animais , Radioisótopos de Carbono/administração & dosagem , Descoberta de Drogas , Fezes/química , Humanos , Masculino , Espectrometria de Massas , Metaboloma , Piridinas/administração & dosagem , Pirimidinas/administração & dosagem , Traçadores Radioativos , Ratos , Ratos Wistar , Contagem de Cintilação , Sensibilidade e Especificidade
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