Accelerator Mass Spectrometry and Bayesian Data Analysis

Accelerator mass spectrometry (AMS) is an ultrasensitive technique for measuring the concentration of a single isotope. The electric and magnetic fields of an electrostatic accelerator system are used to filter out other isotopes from the ion beam. The high velocity means that molecules can be destroyed and removed from the measurement background. As a result, concentrations down to one atom in 10^16 atoms are measurable. This thesis describes the construction of the new AMS system in the Accelerator Laboratory of the University of Helsinki. The system is described in detail along with the relevant ion optics. System performance and some of the 14C measurements done with the system are described. In a second part of the thesis, a novel statistical model for the analysis of AMS data is presented. Bayesian methods are used in order to make the best use of the available information. In the new model, instrumental drift is modelled with a continuous first-order autoregressive process. This enables rigorous normalization to standards measured at different times. The Poisson statistical nature of a 14C measurement is also taken into account properly, so that uncertainty estimates are much more stable. It is shown that, overall, the new model improves both the accuracy and the precision of AMS measurements. In particular, the results can be improved for samples with very low 14C concentrations or measured only a few times.Luonnossa useat prosessit muuttavat alkuaineen isotooppien runsaussuhteita. Näin ollen isotooppien määrän mittaaminen auttaa osaltaan ymmärtämään luonnon prosesseja ja tutkittavan kohteen historiaa. Yksi isotooppien runsaussuhteita muuttava prosessi on radioaktiivisuus. Esimerkiksi radioaktiivisen hiili-14 isotoopin määrä kertoo kuinka kauan eloperäinen näyte on ollut kuolleena tai eristettynä hiilen normaalista kiertokulusta. Luukappaleen, vuosikertaviinin tai vaikkapa ilmakehän aerosolien alkuperää voidaan siis ymmärtää paremmin mittaamalla kohteen hiili-14 pitoisuus. Koska saman alkuaineen eri isotoopit käyttäytyvät kemiallisesti samalla tavoin, harvinaisia isotooppeja voidaan myös käyttää leima-aineina tutkittaville prosesseille kuten lääkeaineiden kulkeutumiselle kehossa. Kiihdytinpohjaisessa massaspektrometriassa hiukkaskiihdytintä käytetään harvinaisten alkuaine-isotooppien runsaussuhteiden mittaamiseen. Kiihdyttimellä saavutettava hiukkasten suuri nopeus mahdollistaa häiritsevien molekyylien poistamisen hiukkassuihkusta törmäyksien avulla. Ei-halutut ionit erotetaan hiukkassuihkusta magneetti- ja sähkökentillä. Tavalliseen massaspektrometriin verrattuna kiihdytinmassaspektrometrillä voidaan mitata yli viisi kertaluokkaa pienempiä pitoisuuksia. Esimerkiksi hiili-14-isotoopin ilmaisukynnys on alle 1:10^15, joka vastaa yhtä milligrammaa hiili-14-isotooppia miljoonassa tonnissa tavallista hiiltä. Tässä väitöskirjatyössä esitellään Helsingin yliopiston fysikaalisten tieteiden laitoksen kiihdytinmassaspektrometri, joka on ensimmäinen laite Suomessa. Nykyinen laitteisto, ionioptiset laskut, kiihdyttimen vaatimat merkittävät muutostyöt sekä mittausten läpivienti kuvataan pääpiirteissään. Lisäksi käydään läpi laitteiston olennaiset ominaisuudet, suorituskyky sekä näiden toteamiseksi suoritetut mittaukset. Laitteen nykyinen tarkkuus on alle prosentin, ja pienin laitteella mitattu hiili-14 runsaussuhde on 4×10^-17, joka vastaa kansainvälisesti parasta tausta-arvoa. Kiihdytinmassaspektrometrian sovellusalueilla luotettavat tulokset ja mittausepävarmuudet ovat ensiarvoisen tärkeitä. Tässä työssä kehitetty bayeslainen tulostenkäsittelymenetelmä parantaa kiihdytinmassaspektrometrian tuloksia merkittävästi keskiarvoistukseen perustuviin menetelmiin verrattuna. Uudessa menetelmässä laitteesta itsestään johtuvaa virhettä kuvataan mukautuvalla autoregressiivisellä prosessilla. Mukautuva prosessi etsii parhaan tavan, jolla mittaustulokset normitetaan standardinäytteiden tuloksiin. Yksittäisten mittaustulosten tiedetään noudattavan Poisson-jakaumaa, joka myös huomioidaan uudessa menetelmässä. Siinä missä otos-pohjaisten menetelmien mittausepävarmuudet heittelevät aiheuttaen virherajojen moninkertaisia ylityksiä, uudessa menetelmässä esitieto virhelähteistä vakauttaa mittausepävarmuudet. Näin tulosten luotettavuus paranee merkittävästi. Myös varsinaisen tuloksen tarkkuus paranee hieman aikaisempiin menetelmiin verrattuna. Lisäksi menetelmä antaa erityisen tarkkoja ja luotettavia tuloksia 1) pienille konsentraatioille, 2) mittauksille joiden välillä on korrelaatioita sekä 3) tapauksille, joissa yhdestä näytteestä voidaan ottaa vain muutamia mittauksia

Seasonal and Diurnal Variations in Atmospheric and Soil Air 14CO2 in a Boreal Scots Pine Forest

We present a radiocarbon (C-14) dataset of tropospheric air CO2 forest soil air CO2, and soil CO2 emissions over the course of one growing season in a Scots pine forest in southern Finland. The CO2 collection for C-14 accelerator mass spectrometry (AMS) analysis was done with a portable, suitcase-sized system, using molecular sieve cartridges to selectively trap CO2 The piloting measurements aimed to quantify the spatial, seasonal and diurnal changes in the C-14 content of CO2 in a northern forest site. The atmospheric samples collected above the canopy showed a large seasonal variation and an 11 parts per thousand difference between day and nighttime profiles in August. The higher Delta C-14 values during night are partly explained by a higher contribution of C-14-elevated soil CO2, accumulating in the nocturnal boundary layer when vertical mixing is weak. We observed significant seasonal trends in Delta C-14-CO2 at different soil depths that reflected changes in the shares of autotrophic and heterotrophic respiration. Also the observed diurnal variation in the Delta C-14 values in soil CO2 highlighted the changes in the origin of CO2, with root activity decreasing more for the night than decomposition.Peer reviewe

Spatial and Temporal Patterns in Black Carbon Deposition to Dated Fennoscandian Arctic Lake Sediments from 1830 to 2010

Peer reviewe

Laser Spectroscopy for Monitoring of Radiocarbon in Atmospheric Samples

In-situ monitoring of radiocarbon emissions is challenging due to the lack of a suitable method for sensitive online detection of this isotope. Here we report on a complete system for automatized continuous on-site monitoring of radiocarbon gaseous emissions from nuclear facilities. By combining radiocarbon detection using mid-infrared cavity ringdown spectroscopy and an advanced sampling system, an elevated amount of radiocarbon in an atmospheric-like gas matrix was detected. Radiocarbon was detected in the form of (CO2)-C-14 after extraction of the carbon dioxide from the air sample. The system is also able to discriminate between radiocarbon in organic or inorganic molecular form by converting (CH4)-C-14 into (CO2)-C-14. This work lays the groundwork for further use of this technology in nuclear facilities for online on-site monitoring of radioactive gaseous emissions as well as future work on in-situ monitoring of atmospheric radiocarbon.Peer reviewe

Tracing Grog and Pots to Reveal Neolithic Corded Ware Culture Contacts in the Baltic Sea Region (SEM-EDS, PIXE)

The Neolithic Corded Ware Culture (CWC) complex spread across the Baltic Sea region ca. 2900/2800-2300/2000 BCE. Whether this cultural adaptation was driven by migration or diffusion remains widely debated. To gather evidence for contact and movement in the CWC material culture, grog-tempered CWC pots from 24 archaeological sites in southern Baltoscandia (Estonia and the southern regions of Finland and Sweden) were sampled for geochemical and micro-structural analyses. Scanning electron microscopy with energy dispersive spectrometry (SEM-EDS) and particle-induced X-ray emission (PIXE) were used for geochemical discrimination of the ceramic fabrics to identify regional CWC pottery manufacturing traditions and ceramic exchange. Major and minor element concentrations in the ceramic body matrices of 163 individual vessels and grog temper (crushed pottery) present in the ceramic fabrics were measured by SEM-EDS. Furthermore, the high-sensitivity PIXE technique was applied for group confirmation. The combined pot and grog matrix data reveal eight geochemical clusters. At least five geochemical groups appeared to be associated with specific find locations and regional manufacturing traditions. The results indicated complex inter-site and cross-Baltic Sea pottery exchange patterns, which became more defined through the grog data, i.e., the previous generations of pots. The CWC pottery exhibited high technological standards at these latitudes, which, together with the identified exchange patterns and the existing evidence of mobility based on human remains elsewhere in the CWC complex, is indicative of the relocation of skilled potters, possibly through exogamy. An analytical protocol for the geochemical discrimination of grog-tempered pottery, and its challenges and possibilities, is presented. (C) 2018 Elsevier Ltd. All rights reserved.Peer reviewe

Ecosystem carbon response of an Arctic peatland to simulated permafrost thaw

Permafrost peatlands are biogeochemical hot spots in the Arctic as they store vast amounts of carbon. Permafrost thaw could release part of these long-term immobile carbon stocks as the greenhouse gases (GHGs) carbon dioxide (CO 2 ) and methane (CH 4 ) to the atmosphere, but how much, at which time-span and as which gaseous carbon species is still highly uncertain. Here we assess the effect of permafrost thaw on GHG dynamics under different moisture and vegetation scenarios in a permafrost peatland. A novel experimental approach using intact plant–soil systems (mesocosms) allowed us to simulate permafrost thaw under near-natural conditions. We monitored GHG flux dynamics via high-resolution flow-through gas measurements, combined with detailed monitoring of soil GHG concentration dynamics, yielding insights into GHG production and consumption potential of individual soil layers. Thawing the upper 10–15 cm of permafrost under dry conditions increased CO 2 emissions to the atmosphere (without vegetation: 0.74 ± 0.49 vs. 0.84 ± 0.60 g CO 2 –C m −2 day −1 ; with vegetation: 1.20 ± 0.50 vs. 1.32 ± 0.60 g CO 2 –C m −2 day −1 , mean ± SD, pre- and post-thaw, respectively). Radiocarbon dating ( 14 C) of respired CO 2 , supported by an independent curve-fitting approach, showed a clear contribution (9%–27%) of old carbon to this enhanced post-thaw CO 2 flux. Elevated concentrations of CO 2 , CH 4 , and dissolved organic carbon at depth indicated not just pulse emissions during the thawing process, but sustained decomposition and GHG production from thawed permafrost. Oxidation of CH 4 in the peat column, however, prevented CH 4 release to the atmosphere. Importantly, we show here that, under dry conditions, peatlands strengthen the permafrost–carbon feedback by adding to the atmospheric CO 2 burden post-thaw. However, as long as the water table remains low, our results reveal a strong CH 4 sink capacity in these types of Arctic ecosystems pre- and post-thaw, with the potential to compensate part of the permafrost CO 2 losses over longer timescales