Stable Isotope and Radiocarbon Analysis for Diet, Climate and Mobility Reconstruction in Agras (Early Iron Age) and Edessa (Roman Age), Northern Greece

In this article we present an isotopic analysis of human bone collagen (δ13Ccol, and δ15Ncol) and bone apatite (δ13C) for diet reconstruction, as well as δ18Oap of human bone apatite for climate reconstruction, using samples from Northern Greece. Radiocarbon dating analysis was conducted on three of the Agras samples and the results (from 1000 to 800 BC) correspond to the Early Iron Age. Isotopic values for δ13Ccol range from −20.5‰ to −16‰ and for δ15Ncol from 6‰ to 11.1‰—a strong indication of a C3-based diet, with contributions by C4 and freshwater fish elements. The results were compared to the ones from Roman Edessa, and Alexandreia (a contemporary city near Edessa), as well as to other Early Iron sites in Greece and wider Europe. In general, the results from Agras are in good agreement with the results from Northern Greece, with the exception of the Makriyalos site, and are quite close to those of Croatia’s and Hungary’s sites. Additionally, from the δ18Oap results we calculated the oxygen isotopic composition of consumed water for Agras (from −9.6‰ to −10.9‰) and for Roman Edessa (from −9.6‰ to −11.2‰) for the palaeoclimate and palaeomobility reconstruction.

The Potential of Tufa as a Tool for Paleoenvironmental Research—A Study of Tufa from the Zrmanja River Canyon, Croatia

Tufa is a fresh-water surface calcium carbonate deposit precipitated at or near ambient temperature, and commonly contains the remains of macro- and microphytes. Many Holocene tufas are found along the Zrmanja River, Dalmatian karst, Croatia. In this work we present radiocarbon dating results of older tufa that was found for the first time at the Zrmanja River near the Village of Sanaderi. Tufa outcrops were observed at different levels, between the river bed and up to 26 m above its present level. Radiocarbon dating of the carbonate fraction revealed ages from modern, at the river bed, up to 40 kBP ~20 m above its present level. These ages fit well with the hypothesis that the Zrmanja River had a previous surface connection with the Krka River, and changed its flow direction toward the Novigrad Sea approximately 40 kBP (Marine Isotope Stage 3). Radiocarbon AMS dating of tufa organic residue yielded a maximum conventional age of 17 kBP for the highest outcrop position indicating probable penetration of younger organic material to hollow tufa structures, as confirmed by radiocarbon analyses of humin extracted from the samples. Stable carbon isotope composition (δ13C) of the carbonate fraction of (−10.4 ± 0.6)‰ and (−9.7 ± 0.8)‰ for the Holocene and the older samples, respectively, indicate the autochthonous origin of the carbonate. The δ13C values of (−30.5 ± 0.3)‰ and (−29.6 ± 0.6)‰ for organic residue, having ages <500 BP and >5000 BP, respectively, suggest a unique carbon source for photosynthesis, mainly atmospheric CO2, with an indication of the Suess effect in δ13C during last centuries. The oxygen isotopic composition (δ18O) agrees well with deposition of tufa samples in two stages, the Holocene (−8.02 ± 0.72‰) and “old” (mainly MIS 3 and the beginning of MIS 2) (−6.89 ± 0.34‰), suggesting a ~4 °C lower temperature in MIS 3 compared to the current one.

Abrupt Heinrich Stadial 1 cooling missing in Greenland oxygen isotopes

Abrupt climate changes during the last deglaciation have been well preserved in proxy records across the globe. However, one long-standing puzzle is the apparent absence of the onset of the Heinrich Stadial 1 (HS1) cold event around 18 ka in Greenland ice core oxygen isotope δ18O records, inconsistent with other proxies. Here, combining proxy records with an isotope-enabled transient deglacial simulation, we propose that a substantial HS1 cooling onset did indeed occur over the Arctic in winter. However, this cooling signal in the depleted oxygen isotopic composition is completely compensated by the enrichment because of the loss of winter precipitation in response to sea ice expansion associated with AMOC slowdown during extreme glacial climate. In contrast, the Arctic summer warmed during HS1 and YD because of increased insolation and greenhouse gases, consistent with snowline reconstructions. Our work suggests that Greenland δ18O may substantially underestimate temperature variability during cold glacial conditions.

A CO2 greenhouse efficiently warmed the early Earth and decreased seawater 18O/16O before the onset of plate tectonics

The low 18O/16O stable isotope ratios (δ18O) of ancient chemical sediments imply ∼70 °C Archean oceans if the oxygen isotopic composition of seawater (sw) was similar to modern values. Models suggesting lower δ18Osw of Archean seawater due to intense continental weathering and/or low degrees of hydrothermal alteration are inconsistent with the triple oxygen isotope composition (Δ’17O) of Precambrian cherts. We show that high CO2 sequestration fluxes into the oceanic crust, associated with extensive silicification, lowered the δ18Osw of seawater on the early Earth without affecting the Δ’17O. Hence, the controversial long-term trend of increasing δ18O in chemical sediments over Earth’s history partly reflects increasing δ18Osw due to decreasing atmospheric pCO2. We suggest that δ18Osw increased from about −5‰ at 3.2 Ga to a new steady-state value close to −2‰ at 2.6 Ga, coinciding with a profound drop in pCO2 that has been suggested for this time interval. Using the moderately low δ18Osw values, a warm but not hot climate can be inferred from the δ18O of the most pristine chemical sediments. Our results are most consistent with a model in which the “faint young Sun” was efficiently counterbalanced by a high-pCO2 greenhouse atmosphere before 3 Ga.

Oxygen isotopes in terrestrial gastropod shells track Quaternary climate change in the American Southwest

Recent studies have shown the oxygen isotopic composition (δ18O) of modern terrestrial gastropod shells is determined largely by the δ18O of precipitation. This implies that fossil shells could be used to reconstruct the δ18O of paleo-precipitation as long as the isotopic system, including the hydrologic pathways of the local watershed and the gastropod systematics, is well understood. In this study, we measured the δ18O values of 456 individual gastropod shells collected from paleowetland deposits in the San Pedro Valley, Arizona that range in age from ca. 29.1 to 9.8 ka. Isotopic differences of up to 2‰ were identified among the four taxa analyzed (Succineidae, Pupilla hebes, Gastrocopta tappaniana, and Vallonia gracilicosta), with Succineidae shells yielding the highest values and V. gracilicosta shells exhibiting the lowest values. We used these data to construct a composite isotopic record that incorporates these taxonomic offsets, and found shell δ18O values increased by ~4‰ between the last glacial maximum and early Holocene, which is similar to the magnitude, direction, and rate of isotopic change recorded by speleothems in the region. These results suggest the terrestrial gastropods analyzed here may be used as a proxy for past climate in a manner that is complementary to speleothems, but potentially with much greater spatial coverage.

Dating of an East Antarctic ice core (GV7) by high resolution chemical stratigraphies

Ice core dating is the first step for a correct interpretation of climatic and environmental changes. In this work, we release a stratigraphic dating of the uppermost 197 m of the 250 m deep GV7(B) ice core (drilling site, 70°41’S, 158°52’E, 1950 m a.s.l.) with a sub-annual resolution. Chemical stratigraphies of NO3−, MSA (methanesulfonic acid), non-sea salt SO42−, sea-salt ions and the oxygen isotopic composition (δ18O) were used in the annual layer counting upon the identification of a seasonal profile in their records. Different procedures were tested and thanks to the volcanic history of the core, obtained in previous works, an accurate age-depth correlation was obtained for the period 1179–2009 CE. Once the dating of the core was finalized, the annual mean accumulation rate was evaluated throughout the analyzed 197 m of the core, obtaining an annually resolved history of the snow accumulation on site in the last millennium. A small, yet consistent, rise in accumulation rate was found for the last 830 years since the middle of the 18th century.

Formation temperature and ages of the True North orogenic gold deposit in Manitoba, Canada

The True North orogenic gold deposit is situated in the 2.99-2.70 Ga Rice Lake greenstone belt near Bissett (Manitoba, Canada). This belt is the western equivalent of northern Ontario's Abitibi gold-producing region. The lithology and alteration, structural control, geochronological framework, and ore geology of the True North orogenic gold deposit have been addressed, but its formation temperature and age are poorly constrained.The deposit's gold-bearing veins are composed mostly of quartz (40 to 80%), ankerite (20 to 30%), and albite (5 to 25%), with minor muscovite, sericite, chlorite, and calcite. Sulfide minerals are dominated by pyrite and chalcopyrite and with minor pyrrhotite; native gold appears as inclusions in sulfides or as free gold. In general, most of the major minerals, the sulfides, and gold all precipitated during the main ore stage.The oxygen isotopic composition of co-existing quartz-albite and quartz-ankerite couples were used to calculate a formation temperature of approximately 230 °C for these minerals, which is comparable to the nearby 007 gold deposit. These temperatures are on the low end of the temperature range reported for orogenic gold deposits. 40Ar/39Ar geochronology (single grain laser fusion of muscovite and sericite) revealed the presence of two age groups, at 2441.2 ± 8.8 Ma and 2483.1 ± 10.2 Ma, approximately 200 My lower than the age of the main collision-related deformation within the Rice Lake belt. These ages indicate that the True North deposit was clearly post-orogenic, similar to vein gold deposits elsewhere, and was likely produced by the emplacement of the Huronian Supergroup and the thermal effects of the Matachewan LIP which has the same ages. It is suggested that the True North deposit may belong to a descriptive category of post-orogenic low-temperature quartz-carbonate-albite vein gold deposit, more in line with recent developments in classification schemes.

δ2Hn-alkane and δ18Osugar biomarker proxies from leaves and topsoils of the Bale Mountains, Ethiopia, and implications for paleoclimate reconstructions

The hydrogen isotopic composition of leaf wax–derived n-alkane (δ2Hn-alkane) and oxygen isotopic composition of hemicellulose–derived sugar (δ18Osugar) biomarkers are valuable proxies for paleoclimate reconstructions. Here, we present a calibration study along the Bale Mountains in Ethiopia to evaluate how accurately and precisely the isotopic composition of precipitation is imprinted in these biomarkers. n-Alkanes and sugars were extracted from the leaf and topsoil samples and compound–specific δ2Hn-alkane and δ18Osugar values were measured using a gas chromatograph–thermal conversion–isotope ratio mass spectrometer (GC–TC–IRMS). The weighted mean δ2Hn-alkane and δ18Osugar values range from − 186 to − 89‰ and from + 27 to + 46‰, respectively. Degradation and root inputs did not appear to alter the isotopic composition of the biomarkers in the soil samples analyzed. Yet, the δ2Hn-alkane values show a statistically significant species dependence and δ18Osugar yielded the same species–dependent trends. The reconstructed leaf water of Erica arborea and Erica trimera is 2H– and 18O–enriched by + 55 ± 5 and + 9 ± 1‰, respectively, compared to precipitation. By contrast, Festuca abyssinica reveals the most negative δ2Hn-alkane and least positive δ18Osugar values. This can be attributed to “signal–dampening” caused by basal grass leaf growth. The intermediate values for Alchemilla haumannii and Helichrysum splendidum can be likely explained with plant physiological differences or microclimatic conditions affecting relative humidity (RH) and thus RH–dependent leaf water isotope enrichment. While the actual RH values range from 69 to 82% (x̄ = 80 ± 3.4%), the reconstructed RH values based on a recently suggested coupled δ2Hn-alkane –δ18Osugar (paleo–) hygrometer approach yielded a mean of 78 ± 21%. Our findings corroborate (i) that vegetation changes, particularly in terms of grass versus non–grassy vegetation, need to be considered in paleoclimate studies based on δ2Hn-alkane and δ18Osugar records and (ii) that the coupled δ2Hn-alkane –δ18Osugar (paleo–) hygrometer approach holds great potential for deriving additional paleoclimatic information compared to single isotope approaches.