Emerging nuclear methods for historical painting authentication: AMS-14C dating, MeV-SIMS and O-PTIR imaging, global IBA, differential-PIXE and full-field PIXE mapping.

There is a considerable interest in developing new analytical tools to fight the illicit trafficking of heritage goods and particularly of easel paintings, whose high market values attract an ever-increasing volume of criminal activities. The objective is to combat the illicit traffic of smuggled or forged paintworks and to prevent the acquisition of fakes or looted artefacts in public collections. Authentication can be addressed using various investigation techniques, such as absolute dating, materials characterization, alteration phenomena, etc.; for paintings this remains a challenging task due to the complexity of the materials (paint layers, ground, varnish, canvas, etc.) and preferable use of non-destructive methods. This paper outlines results from concerted action on detecting forged works of art within the framework of a Coordinated Research Project of the International Atomic Energy Agency (IAEA) called Enhancing Nuclear Analytical Techniques to Meet the Needs of Forensic Sciences1. One of the main objectives is to foster the use of emerging Nuclear Analytical Techniques (NAT) using particle accelerators for authentication of paintings, with potential application to other forensics domains, by highlighting their ability to determine painting authenticity and to track restorations or anachronistic clues. The various materials comprising a test painting were investigated using an array of NAT. Binder, canvas and support were directly dated by 14C using Accelerator Mass Spectrometry (14C-AMS); binder and pigments' molecular composition was determined using Secondary Ion Mass Spectrometry with MeV ions (MeV-SIMS); paint layer composition and stratigraphy were accurately determined using Ion Beam Analysis (IBA) and differential Particle-Induced X-ray Emission (PIXE); and pigment spatial distributions were mapped using full-field PIXE. High resolution Optical Photothermal Infrared Spectroscopy (O-PTIR) molecular imaging was also exploited. Obtained results are presented and discussed. It is shown that the combination of the above-mentioned techniques allowed reconstructing the history of the test painting.

Recurrent transitions to Little Ice Age-like climatic regimes over the Holocene.

Holocene climate variability is punctuated by episodic climatic events such as the Little Ice Age (LIA) predating the industrial-era warming. Their dating and forcing mechanisms have however remained controversial. Even more crucially, it is uncertain whether earlier events represent climatic regimes similar to the LIA. Here we produce and analyse a new 7500-year long palaeoclimate record tailored to detect LIA-like climatic regimes from northern European tree-ring data. In addition to the actual LIA, we identify LIA-like ca. 100-800 year periods with cold temperatures combined with clear sky conditions from 540 CE, 1670 BCE, 3240 BCE and 5450 BCE onwards, these LIA-like regimes covering 20% of the study period. Consistent with climate modelling, the LIA-like regimes originate from a coupled atmosphere-ocean-sea ice North Atlantic-Arctic system and were amplified by volcanic activity (multiple eruptions closely spaced in time), tree-ring evidence pointing to similarly enhanced LIA-like regimes starting after the eruptions recorded in 1627 BCE, 536/540 CE and 1809/1815 CE. Conversely, the ongoing decline in Arctic sea-ice extent is mirrored in our data which shows reversal of the LIA-like conditions since the late nineteenth century, our record also correlating highly with the instrumentally recorded Northern Hemisphere and global temperatures over the same period. Our results bridge the gaps between low- and high-resolution, precisely dated proxies and demonstrate the efficacy of slow and fast components of the climate system to generate LIA-like climate regimes. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s00382-021-05669-0.

Observed and Modeled Black Carbon Deposition and Sources in the Western Russian Arctic 1800-2014.

Black carbon (BC) particles contribute to climate warming by heating the atmosphere and reducing the albedo of snow/ice surfaces. The available Arctic BC deposition records are restricted to the Atlantic and North American sectors, for which previous studies suggest considerable spatial differences in trends. Here, we present first long-term BC deposition and radiocarbon-based source apportionment data from Russia using four lake sediment records from western Arctic Russia, a region influenced by BC emissions from oil and gas production. The records consistently indicate increasing BC fluxes between 1800 and 2014. The radiocarbon analyses suggest mainly (∼70%) biomass sources for BC with fossil fuel contributions peaking around 1960-1990. Backward calculations with the atmospheric transport model FLEXPART show emission source areas and indicate that modeled BC deposition between 1900 and 1999 is largely driven by emission trends. Comparison of observed and modeled data suggests the need to update anthropogenic BC emission inventories for Russia, as these seem to underestimate Russian BC emissions and since 1980s potentially inaccurately portray their trend. Additionally, the observations may indicate underestimation of wildfire emissions in inventories. Reliable information on BC deposition trends and sources is essential for design of efficient and effective policies to limit climate warming.

Ancient Bacterial Genomes Reveal a High Diversity of Treponema pallidum Strains in Early Modern Europe.

Syphilis is a globally re-emerging disease, which has marked European history with a devastating epidemic at the end of the 15th century. Together with non-venereal treponemal diseases, like bejel and yaws, which are found today in subtropical and tropical regions, it currently poses a substantial health threat worldwide. The origins and spread of treponemal diseases remain unresolved, including syphilis' potential introduction into Europe from the Americas. Here, we present the first genetic data from archaeological human remains reflecting a high diversity of Treponema pallidum in early modern Europe. Our study demonstrates that a variety of strains related to both venereal syphilis and yaws-causing T. pallidum subspecies were already present in Northern Europe in the early modern period. We also discovered a previously unknown T. pallidum lineage recovered as a sister group to yaws- and bejel-causing lineages. These findings imply a more complex pattern of geographical distribution and etiology of early treponemal epidemics than previously understood.

Buried in water, burdened by nature-Resilience carried the Iron Age people through Fimbulvinter.

Levänluhta is a unique archaeological site with the remains of nearly a hundred Iron Age individuals found from a water burial in Ostrobothnia, Finland. The strongest climatic downturn of the Common Era, resembling the great Fimbulvinter in Norse mythology, hit these people during the 6th century AD. This study establishes chronological, dietary, and livelihood synthesis on this population based on stable carbon and nitrogen isotopic and radiocarbon analyses on human remains, supported by multidisciplinary evidence. Extraordinarily broad stable isotopic distribution is observed, indicating three subgroups with distinct dietary habits spanning four centuries. This emphasizes the versatile livelihoods practiced at this boundary of marine, freshwater, and terrestrial ecosystems. While the impact of the prolonged cold darkness of the 6th century was devastating for European communities relying on cultivation, the broad range of livelihoods provided resilience for the Levänluhta people to overcome the abrupt climatic decline.

Human mitochondrial DNA lineages in Iron-Age Fennoscandia suggest incipient admixture and eastern introduction of farming-related maternal ancestry.

Human ancient DNA studies have revealed high mobility in Europe's past, and have helped to decode the human history on the Eurasian continent. Northeastern Europe, especially north of the Baltic Sea, however, remains less well understood largely due to the lack of preserved human remains. Finland, with a divergent population history from most of Europe, offers a unique perspective to hunter-gatherer way of life, but thus far genetic information on prehistoric human groups in Finland is nearly absent. Here we report 103 complete ancient mitochondrial genomes from human remains dated to AD 300-1800, and explore mtDNA diversity associated with hunter-gatherers and Neolithic farmers. The results indicate largely unadmixed mtDNA pools of differing ancestries from Iron-Age on, suggesting a rather late genetic shift from hunter-gatherers towards farmers in North-East Europe. Furthermore, the data suggest eastern introduction of farmer-related haplogroups into Finland, contradicting contemporary genetic patterns in Finns.

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 ring-down 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 14CO2 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 14CH4 into 14CO2. 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.

Uptake of Soil-Derived Carbon into Plants: Implications for Disposal of Nuclear Waste.

Radiocarbon (14C) is potentially significant in terms of release from deep geological disposal of radioactive waste and incorporation into the biosphere. In this study we investigated the transfer of soil-derived C into two plant species by using a novel approach, where the uptake of soil-derived C into newly cultivated plants was studied on 8000-year leftover peat in order to distinguish between soil-derived and atmospheric C. Two-pool isotope mixing model was used to reveal the fraction of soil C in plants. Our results indicated that although the majority of plant C was obtained from atmosphere by photosynthesis, a significant portion (up to 3-5%) of C in plant roots was derived from old soil. We found that uptake of soil C into roots was more pronounced in ectomycorrhizal Scots pine than in endomycorrhizal reed canary grass, but nonetheless, both species showed soil-derived C uptake in their roots. Although plenty of soil-derived C was available in canopy air for reassimilation by photosynthesis, no trace of soil-derived C was detected in aboveground parts, possibly due to the open canopy. The results suggest that the potential for contamination with 14C is higher for roots than for leaves.

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 (CO2 ) and methane (CH4 ) 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 CO2 emissions to the atmosphere (without vegetation: 0.74 ± 0.49 vs. 0.84 ± 0.60 g CO2 -C m-2  day-1 ; with vegetation: 1.20 ± 0.50 vs. 1.32 ± 0.60 g CO2 -C m-2  day-1 , mean ± SD, pre- and post-thaw, respectively). Radiocarbon dating (14 C) of respired CO2 , supported by an independent curve-fitting approach, showed a clear contribution (9%-27%) of old carbon to this enhanced post-thaw CO2 flux. Elevated concentrations of CO2 , CH4 , 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 CH4 in the peat column, however, prevented CH4 release to the atmosphere. Importantly, we show here that, under dry conditions, peatlands strengthen the permafrost-carbon feedback by adding to the atmospheric CO2 burden post-thaw. However, as long as the water table remains low, our results reveal a strong CH4 sink capacity in these types of Arctic ecosystems pre- and post-thaw, with the potential to compensate part of the permafrost CO2 losses over longer timescales.

Author Correction: The genetic prehistory of the Baltic Sea region.

The original version of this Article omitted references to previous work, which are detailed in the associated Author Correction. These omissions have been corrected in both the PDF and HTML versions of the Article.

The genetic prehistory of the Baltic Sea region.

While the series of events that shaped the transition between foraging societies and food producers are well described for Central and Southern Europe, genetic evidence from Northern Europe surrounding the Baltic Sea is still sparse. Here, we report genome-wide DNA data from 38 ancient North Europeans ranging from ~9500 to 2200 years before present. Our analysis provides genetic evidence that hunter-gatherers settled Scandinavia via two routes. We reveal that the first Scandinavian farmers derive their ancestry from Anatolia 1000 years earlier than previously demonstrated. The range of Mesolithic Western hunter-gatherers extended to the east of the Baltic Sea, where these populations persisted without gene-flow from Central European farmers during the Early and Middle Neolithic. The arrival of steppe pastoralists in the Late Neolithic introduced a major shift in economy and mediated the spread of a new ancestry associated with the Corded Ware Complex in Northern Europe.

Arctic moistening provides negative feedbacks to riparian plants.

Arctic moistening will affect the circumpolar forested riparian ecosystems. Upward trends observed for precipitation in high latitudes illustrate that the moistening may be underway to influence the woody biomass production near the inland waters, lakes and streams with effects on carbon pools and fluxes. Although the flooding and waterlogging tolerance of seedlings has been investigated, our understanding of responses in mature trees is still limited. Here we employ tree-ring δ13 C and width data from a subarctic riparian setting in Lapland, where artificially high lake level (HLL) has already altered the ecophysiological and growth responses of riparian Pinus sylvestris trees to external drivers under conditions simulating moister environment. Prior to the HLL event, the carbon assimilation rate was primarily limited by irradiance as reflected in the δ13 C data and the radial growth of south-facing riparian trees remained increased in comparison to shaded upland trees. By contrast, the riparian trees were not similarly benefited during the HLL period when reduced assimilation depleted the riparian in comparison to upland δ13 C despite of increased irradiance. As a result, the radial growth of riparian trees was markedly reduced over the HLL event while the upland trees benefited from increased irradiance and summer time warming. Although the production of biomass at high latitudes is commonly considered temperature-limited, our results highlight the increasing role of Arctic moistening to limit the growth when increased precipitation (cloudiness) reduces the incoming solar radiation in general and when the riparian habitat becomes increasingly waterlogged in particular. The effects of high-latitude warming to induce higher biomass productivity may be restricted by negative feedbacks.

Volcanic dust veils from sixth century tree-ring isotopes linked to reduced irradiance, primary production and human health.

The large volcanic eruptions of AD 536 and 540 led to climate cooling and contributed to hardships of Late Antiquity societies throughout Eurasia, and triggered a major environmental event in the historical Roman Empire. Our set of stable carbon isotope records from subfossil tree rings demonstrates a strong negative excursion in AD 536 and 541-544. Modern data from these sites show that carbon isotope variations are driven by solar radiation. A model based on sixth century isotopes reconstruct an irradiance anomaly for AD 536 and 541-544 of nearly three standard deviations below the mean value based on modern data. This anomaly can be explained by a volcanic dust veil reducing solar radiation and thus primary production threatening food security over a multitude of years. We offer a hypothesis that persistently low irradiance contributed to remarkably simultaneous outbreaks of famine and Justinianic plague in the eastern Roman Empire with adverse effects on crop production and photosynthesis of the vitamin D in human skin and thus, collectively, human health. Our results provide a hitherto unstudied proxy for exploring the mechanisms of 'volcanic summers' to demonstrate the post-eruption deficiencies in sunlight and to explain the human consequences during such calamity years.

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

Black carbon (BC) is fine particulate matter produced by the incomplete combustion of biomass and fossil fuels. It has a strong climate warming effect that is amplified in the Arctic. Long-term trends of BC play an important role in assessing the climatic effects of BC and in model validation. However, few historical BC records exist from high latitudes. We present five lake-sediment soot-BC (SBC) records from the Fennoscandian Arctic and compare them with records of spheroidal carbonaceous fly-ash particles (SCPs), another BC component, for ca. the last 120 years. The records show spatial and temporal variation in SBC fluxes. Two northernmost lakes indicate declining values from 1960 to the present, which is consistent with modeled BC deposition and atmospheric measurements in the area. However, two lakes located closer to the Kola Peninsula (Russia) have recorded increasing SBC fluxes from 1970 to the present, which is likely caused by regional industrial emissions. The increasing trend is in agreement with a Svalbard ice-core-BC record. The results suggest that BC deposition in parts of the European Arctic may have increased over the last few decades, and further studies are needed to clarify the spatial extent of the increasing BC values and to ascertain the climatic implications.

Radiocarbon dating of fluvial organic matter reveals land-use impacts in boreal peatlands.

This study measured the effects of land use on organic matter released to surface waters in a boreal peat catchment using radiocarbon dating of particulate and dissolved organic carbon (POC and DOC), DOC concentration, stable carbon and nitrogen isotope composition, and optical measurements. Undisturbed sites invariably released modern DOC and POC (<20 years old), and seasonal forcing had little impact on the age distribution. Release of pre-1950 carbon was detected at peat extraction, agricultural and drained sites, and was consistently observed at agricultural and peat extraction areas throughout the seasons. Conventional mean DOC ages reached 3,100 (±122) years before collection. On average, DOC concentrations were up to 38% higher at impacted sites compared to natural areas, but there was no significant effect of land use on surface water DOC concentrations. The study indicates that the true extent of land use impacts is not necessarily detectible through changes in DOC concentration alone: Radiocarbon dating was essential to show that leaching of old soil organic matter at modified sites had replaced, rather than supplemented, the modern DOM that is usually released from pristine peatlands. Relationships between the specific fluorescence intensity of DOM and its radiocarbon age were identified, indicating that optical techniques may provide a method for the detection of changes in DOM age.

Neolithic dairy farming at the extreme of agriculture in northern Europe.

The conventional 'Neolithic package' comprised animals and plants originally domesticated in the Near East. As farming spread on a generally northwest trajectory across Europe, early pastoralists would have been faced with the challenge of making farming viable in regions in which the organisms were poorly adapted to providing optimal yields or even surviving. Hence, it has long been debated whether Neolithic economies were ever established at the modern limits of agriculture. Here, we examine food residues in pottery, testing a hypothesis that Neolithic farming was practiced beyond the 60th parallel north. Our findings, based on diagnostic biomarker lipids and δ(13)C values of preserved fatty acids, reveal a transition at ca 2500 BC from the exploitation of aquatic organisms to processing of ruminant products, specifically milk, confirming farming was practiced at high latitudes. Combining this with genetic, environmental and archaeological information, we demonstrate the origins of dairying probably accompanied an incoming, genetically distinct, population successfully establishing this new subsistence 'package'.

Temperature sensitivity of soil carbon fractions in boreal forest soil.

Feedback to climate warming from the carbon balance of terrestrial ecosystems depends critically on the temperature sensitivity of soil organic carbon (SOC) decomposition. Still, the temperature sensitivity is not known for the majority of the SOC, which is tens or hundreds of years old. This old fraction is paradoxically concluded to be more, less, or equally sensitive compared to the younger fraction. Here, we present results that explain these inconsistencies. We show that the temperature sensitivity of decomposition increases remarkably from the youngest annually cycling fraction (Q10 < 2) to a decadally cycling one (Q10 = 4.2-6.9) but decreases again to a centennially cycling fraction (Q10 = 2.4-2.8) in boreal forest soil. Compared to the method used for current global estimates (temperature sensitivity of all SOC equal to that of the total heterotrophic soil respiration), the soils studied will lose 30-45% more carbon in response to climate warming during the next few decades, if there is no change in carbon input. Carbon input, derivative of plant productivity, would have to increase by 100-120%, as compared to the earlier estimated 70-80%, in order to compensate for the accelerated decomposition.