Late Holocene (~ 2 ka) East Asian Monsoon variations inferred from river discharge and climate interrelationships in the Pearl River Estuary

A sediment core from the Pearl River Estuary (PRE) was analyzed for grain size and organic geochemistry parameters (TOC and δ¹³C_org). The results showed that high mean grain-size value and increased sand content were correlated with the high TOC and negative δ¹³C_org. These results indicated high river runoff in the PRE area. Peak river discharge occurred during the periods 1900–1750, 1500–1600, 1400–1200, 1000–900 and 750–600 cal yr BP. The main changes recorded in grain-size distributions, TOC contents, and δ¹³C_org variations appear to be directly related to monsoon precipitation in the sediment source area. An increased East Asian summer monsoon rainfall (EASM) and/or an enhanced East Asian winter monsoon rainfall could result in the increasing of monsoon rainfall. Typhoon related rainfalls could act as positive influence on precipitation levels. The study of the correlations between the rainfall records and ENSO activities revealed a close relationship between the monsoon rainfall in the PRE and the tropical Pacific variations. The frequent occurrence of ENSO might result in the southern migration of the EASM rain belt and lead to more typhoon-derived rainfall in the PRD during the late Holocene.     

Deciphering late Quaternary land snail shell δO and δC from Franchthi Cave (Argolid,Greece)

This paper investigates the stable isotopic composition from late Pleistocene–Holocene (~ 13 to ~ 10.5 cal ka BP) shells of the land snail Helix figulina, from Franchthi Cave (Greece). It explores the palaeoclimatic and palaeoenvironmental implications of the isotope palaeoecology of archaeological shells at the time of human occupation of the cave. Modern shells from around the cave were also analysed and their isotopic signatures compared with those of the archaeological shells. The carbon isotope composition of modern shells depicts the consumption of C₃ vegetation. Shell oxygen isotopic values are consistent with other Mediterranean snail shells from coastal areas. Combining empirical linear regression and an evaporative model, the δ¹⁸Os suggest that modern snails in the study area are active during periods of higher relative humidity and lower rainfall δ¹⁸O, probably at night. Late glacial and early Holocene δ¹⁸Os show lower values compared to modern ones. Early Holocene δ¹⁸Os values likely track enhanced moisture and isotopic changes in the precipitation source. By contrast, lower late glacial δ¹⁸O could reflect lower temperatures and δ¹⁸Op, compared to the present day. Shell carbon isotope values indicate the presence of C₃ vegetation as main source of carbon to late glacial and early Holocene snails.     

Holocene fire occurrence and alluvial responses at the leading edge of pinyon–juniper migration in the Northern Great Basin,USA

Fire and vegetation records at the City of Rocks National Reserve (CIRO), south-central Idaho, display the interaction of changing climate, fire and vegetation along the migrating front of single-leaf pinyon (Pinus monophylla) and Utah juniper (Juniperus osteosperma). Radiocarbon dating of alluvial charcoal reconstructed local fire occurrence and geomorphic response, and fossil woodrat (Neotoma) middens revealed pinyon and juniper arrivals. Fire peaks occurred ~ 10,700–9500, 7200–6700, 2400–2000, 850–700, and 550–400 cal yr BP, whereas ~ 9500–7200, 6700–4700 and ~ 1500–1000 cal yr BP are fire-free. Wetter climates and denser vegetation fueled episodic fires and debris flows during the early and late Holocene, whereas drier climates and reduced vegetation caused frequent sheetflooding during the mid-Holocene. Increased fires during the wetter and more variable late Holocene suggest variable climate and adequate fuels augment fires at CIRO. Utah juniper and single-leaf pinyon colonized CIRO by 3800 and 2800 cal yr BP, respectively, though pinyon did not expand broadly until ~ 700 cal yr BP. Increased fire-related deposition coincided with regional droughts and pinyon infilling ~ 850–700 and 550–400 cal yr BP. Early and late Holocene vegetation change probably played a major role in accelerated fire activity, which may be sustained into the future due to pinyon–juniper densification and cheatgrass invasion.     

Carbon and oxygen stable isotope compositions of late Pleistocene mammal teeth from dolines of Ajoie (Northwestern Switzerland)

Fossils of megaherbivores from eight late Pleistocene ¹⁴C- and OSL-dated doline infillings of Ajoie (NW Switzerland) were discovered along the Transjurane highway in the Swiss Jura. Carbon and oxygen analyses of enamel were performed on forty-six teeth of large mammals (Equus germanicus, Mammuthus primigenius, Coelodonta antiquitatis, and Bison priscus), coming from one doline in Boncourt (~ 80 ka, marine oxygen isotope stage MIS5a) and seven in Courtedoux (51–27 ka, late MIS3), in order to reconstruct the paleoclimatic and paleoenvironmental conditions of the region. Similar enamel δ¹³C values for both periods, ranging from − 14.5 to − 9.2‰, indicate that the megaherbivores lived in a C₃ plant-dominated environment. Enamel δ¹⁸O_PO4 values range from 10.9 to 16.3‰ with a mean of 13.5 ± 1.0‰ (n = 46). Mean air temperatures (MATs) were inferred using species-specific δ¹⁸O_PO4–δ¹⁸O_H2O-calibrations for modern mammals and a present-day precipitation δ¹⁸O_H2O-MAT relation for Switzerland. Similar average MATs of 6.6 ± 3.6°C for the deposits dated to ~ 80 ka and 6.5 ± 3.3°C for those dated to the interval 51–27 ka were estimated. This suggests that these mammals in the Ajoie area lived in mild periods of the late Pleistocene with MATs only about 2.5°C lower than modern-day temperatures.     

Paleoclimate record in the Nubian Sandstone Aquifer,Sinai Peninsula,Egypt

Sixteen groundwater samples collected from production wells tapping Lower Cretaceous Nubian Sandstone and fractured basement aquifers in Sinai were analyzed for their stable isotopic compositions, dissolved noble gas concentrations (recharge temperatures), tritium activities, and ¹⁴C abundances. Results define two groups of samples: Group I has older ages, lower recharge temperatures, and depleted isotopic compositions (adjusted ¹⁴C model age: 24,000–31,000 yr BP; δ¹⁸O: − 9.59‰ to − 6.53‰; δ²H: − 72.9‰ to − 42.9‰; < 1 TU; and recharge T: 17.5–22.0°C) compared to Group II (adjusted ¹⁴C model age: 700–4700 yr BP; δ¹⁸O: − 5.89‰ to − 4.84‰; δ²H: − 34.5‰ to − 24.1‰; < 1 to 2.78 TU; and recharge T: 20.6–26.2°C). Group II samples have isotopic compositions similar to those of average modern rainfall, with larger d-excess values than Group I waters, and locally measurable tritium activity (up to 2.8 TU). These observations are consistent with (1) the Nubian Aquifer being largely recharged prior to and/or during the Last Glacial Maximum (represented by Group I), possibly through the intensification of paleowesterlies; and (2) continued sporadic recharge during the relatively dry and warmer interglacial period (represented by Group II) under conditions similar to those of the present.     

Geochronology and paleoenvironment of pluvial Harper Lake,Mojave Desert,California, USA

Accurate reconstruction of the paleo-Mojave River and pluvial lake (Harper, Manix, Cronese, and Mojave) system of southern California is critical to understanding paleoclimate and the North American polar jet stream position over the last 500 ka. Previous studies inferred a polar jet stream south of 35°N at 18 ka and at ~ 40°N at 17–14 ka. Highstand sediments of Harper Lake, the upstream-most pluvial lake along the Mojave River, have yielded uncalibrated radiocarbon ages ranging from 24,000 to > 30,000 ¹⁴C yr BP. Based on geologic mapping, radiocarbon and optically stimulated luminescence dating, we infer a ~ 45–40 ka age for the Harper Lake highstand sediments. Combining the Harper Lake highstand with other Great Basin pluvial lake/spring and marine climate records, we infer that the North American polar jet stream was south of 35°N about 45–40 ka, but shifted to 40°N by ~ 35 ka. Ostracodes (Limnocythere ceriotuberosa) from Harper Lake highstand sediments are consistent with an alkaline lake environment that received seasonal inflow from the Mojave River, thus confirming the lake was fed by the Mojave River. The ~ 45–40 ka highstand at Harper Lake coincides with a shallowing interval at downstream Lake Manix.     

Holocene landscape evolution and geoarcheology of low-order streams in the Rio Grande basin,San Juan Mountains,Colorado, USA

This geoarcheological study investigates soil stratigraphy and geochronology of alluvial deposits to determine Holocene landscape evolution within the Hot Creek, La Jara Creek, and Alamosa River drainage basins in the San Juan Mountains of Colorado. Geomorphic mapping and radiocarbon dating indicate synchronicity in patterns of erosion, deposition, and stability between drainage basins. In all three basins, the maximum age of mapped alluvial terraces and fans is ~ 3300 cal yr BP. A depositional period seen at both Hot Creek and the Alamosa River begins ~ 3300 to 3200 cal yr BP. Based on soil development, short periods of stability followed by alluvial fan aggradation occur in the Alamosa River basin ~ 2200 cal yr BP. A period of landscape stability at Hot Creek before ~ 1100 cal yr BP is followed by a period of rapid aggradation within all three drainages between ~ 1100 and 850 cal yr BP. A final aggradation event occurred between ~ 630 and 520 cal yr BP at La Jara Creek. These patterns of landscape evolution over the past ~ 3300 yr provide the framework for an archeological model that predicts the potential for buried and surficial cultural materials in the research area.     

Quantifying seasonal precipitation using high-resolution carbon isotope analyses in evergreen wood

High-resolution natural abundance stable carbon isotope analyses across annual growth rings in evergreen trees reveal a cyclic increase and decrease in the measured carbon isotopic composition (δ¹³C), but the causes of this pattern are poorly understood. We compiled new and published high-resolution δ¹³C data from across annual growth rings of 33 modern evergreen trees from 10 genera and 15 globally distributed sites to quantify the parameters that affect the observed δ¹³C pattern. Across a broad range of latitude, temperature, and precipitation regimes, we found that the average, measured seasonal change in δ¹³C (Δδ¹³C_meas, ‰) within tree rings of evergreen species reflects changes in the carbon isotopic composition of atmospheric carbon dioxide (Δδ¹³C_CO2) and changes in seasonal precipitation (ΔP) according to the following equation: Δδ¹³C_meas = Δδ¹³C_CO2 - 0.82(ΔP) + 0.73; R² = 0.96. Seasonal changes in temperature, pCO₂, and light levels were not found to significantly affect Δδ¹³C_meas. We propose that this relationship can be used to quantify seasonal patterns in paleoprecipitation from intra-ring profiles of δ¹³C measured from non-permineralized, fossil wood.     

Stable isotopes reveal ecological differences amongst now‐extinct proboscideans from the Cincinnati region,USA

The mobility and dietary preferences of now‐extinct proboscideans have not been comprehensively examined in the central USA. We used stable carbon (δ¹³C), oxygen (δ¹⁸O) and strontium (⁸⁷Sr/⁸⁶Sr) isotopic signatures in molar enamel to investigate the foraging ecology of four mastodons (Mammut americanum) and eight mammoths (Mammuthus spp.) from southwestern Ohio and northwestern Kentucky. We tested two hypotheses: (i) these individuals were nomadic migrants that were passing through the region when they died; and (ii) mammoths and mastodons foraged in different environments. Unexpectedly, our results suggest that 11 of the 12 sampled individuals were regional residents. With the exception of one mastodon, ⁸⁷Sr/⁸⁶Sr ratios for proboscideans and regional water samples were statistically indistinguishable; slightly lower ratios for waters suggest glacial loess has an impact on modern samples. Amongst the individuals identified as residents, ⁸⁷Sr/⁸⁶Sr ratios indicate that mammoths and mastodons foraged in discrete geographical areas, and δ¹³C values imply dietary differences between the genera, which is consistent with our expectations. Oxygen isotope values may be able to distinguish animals that lived during the Last Glacial Maximum (LGM) from those that lived more recently. Three mammoths and one mastodon yielded δ¹⁸O values that are similar to modern regional precipitation and surface water, but too high for estimated drinking water during the LGM. We propose that these individuals lived during a relatively warm period following the LGM. Compellingly, the mammoth with the highest δ¹⁸O value also has the lowest δ¹³C value, suggesting that this individual was alive after regional vegetation shifted from open parkland to deciduous forest dominated by C₃ species. Our results demonstrate that a wealth of information can be gleaned from fossil museum specimens and lay a foundation for future work on the foraging ecology of proboscideans and other extinct megafauna from the Midwest USA.     

Controls on dissolved inorganic carbon and δC in cave waters from DeSoto Caverns: Implications for speleothem δC assessments

Unraveling the factors controlling the carbon chemistry and transport of carbon within extant karst systems has important implications concerning the assessment of time-series δ¹³C records of speleothems. Here we report the results of a 3-year study of total dissolved inorganic carbon [DIC] and δ¹³C_DIC from cave waters at DeSoto Caverns (Southeastern USA) that offer valuable insight on carbon transport and the accompanied isotope fractionations from end-member sources to speleothems.[DIC] and δ¹³C_DIC values of cave waters range from 0.2 to 6.0 mM and 2.7 to −12.9 (‰ VPDB), respectively. [DIC] and δ¹³C_DIC of “seasonal drips” show seasonal, albeit noisy, variability and are inversely related (δ¹³C_DIC = −2.49[DIC] + 0.64, r² = 0.84). A shallow pool fed by multiple drips shows a bimodal δ¹³C_DIC distribution with an isotopically heavier mode during winter (−4‰ to −5‰ VPDB) relative to summer months (−9‰ to −10‰ VPDB). A multi-year trend of decreasing water availability during the study period is not reflected in a response of cave water carbon chemistry suggesting that rainfall amount may not be a significant controlling factor of the carbon chemistry. Coupled cave air winter ventilation/summer stagnation and varying CO₂ fluxes through the soil horizon and epikarst exert the strongest influence on seasonal [DIC] and δ¹³C_DIC variability. Measured values of high [DIC] and low δ¹³C_DIC from cave waters collected during the summer/early fall closely approximate isotopic equilibrium conditions. Conversely, low [DIC] and high δ¹³C_DIC values during winter/early months indicate kinetically enhanced isotopic fractionations within the cave waters. The kinetically enhanced isotopic fractionation of partitioned between degassed CO₂ and precipitated CaCO₃(1000lnα_{[(CO2-HCO3)+(CaCO3(AR)-HCO3)]/2}) is greater by about a factor of two (−6.7 ± 0.3‰) relative to the same isotopic fractionation under equilibrium conditions (−3.1‰).On the basis of ¹⁴C mass balance and paired ¹⁴C-U/Th measurements we estimate that on average about ∼23% of C delivered annually by the drips to the aragonite stalagmites is derived from ¹⁴C-dead dolomite cap while the remainder of ∼77% is derived from ¹⁴C-live biomass. δ¹³C measurements of aragonite (n = 12) sampled from the tips of active speleothems during the summer months are consistent with theoretical aragonite δ¹³C values calculated using the shallow pool summer/early fall data thus confirming the δ¹³C seasonality in both drips and coeval aragonite. δ¹³C values of an active stalagmite section spanning the last 200 years show a normal distribution with a mean of −7.1 ± 1.2‰ (n = 81) and a mode of −7‰ to −8‰ that are statistically indistinguishable from the annual mean and mode of all dripwaters. Thus secular time-series δ¹³C records of stalagmites at DeSoto Caverns with resolving power >10⁻¹ year will likely carry the imprints of drip annual means that record climate-driven δ¹³C seasonal biases.     

Late Quaternary environmental change of Yellow River Basin: An organic geochemical record in Bohai Sea (North China)

Bulk geochemical characterization (total organic carbon, grain size distribution, carbon isotope composition) and molecular biomarkers (lignin phenols, straight chain aliphatic hydrocarbons, glycerol dialkyl glycerol tetraethers) were analyzed for a 21 m core from the Bohai Sea (North China), spanning ca 21 ka BP. These paleo-proxies presented remarkable differences between the late glacial period and the Holocene, reflecting continental and coastal environments, respectively. Two peat layers were deposited during the period of ca 9000-8460 yr BP. Thereafter the core site has been consistently covered by seawater until recent reclamation of land from the sea. The occurrence of a total organic carbon maximum from ca 6000-3800 yr BP was attributed to delivery of organic carbon enriched sediments via the Yellow River, consistent with increased vegetation density and higher development of soil under warm and humid mid-Holocene climate conditions. The distributions of lignin phenol compositions and C₃₁/C₂₉n-alkane ratio suggested the largest expansion of woody plants between ca 5300 and 4000 yr BP, corresponding to the extremely favorable climatic conditions. Since ca 3800 yr BP, an abrupt increase in the C₃₁/C₂₉n-alkane ratio suggested higher abundance of grasses, consistent with a drying climate trend after the mid-Holocene. Since our coastal sediments close to the Yellow River outflow contain catchment-integrated environmental signals of the river basin, molecular proxies demonstrate that the variability of vegetation distributions in the Holocene is a widespread phenomenon in those areas adjacent to Yellow River Basin.     

Sources of carbon isotope variation in kangaroo bone collagen and tooth enamel

The stable carbon isotopic composition (expressed as δ¹³C) of herbivore remains is commonly used to reconstruct past changes in the relative abundance of C₄ versus C₃ grass biomass (C₄ relative abundance). However, the strength of the relationship between herbivore δ¹³C and C₄ relative abundance in extant ecosystems has not been thoroughly examined. We determined sources of variation in δ¹³C of bone collagen and tooth enamel of kangaroos (Macropus spp.) collected throughout Australia by measuring δ¹³C of bone collagen (779 individuals) and tooth enamel (694 individuals). An index of seasonal water availability, i.e. the distribution of rainfall in the C₄ versus C₃ growing seasons, was used as a proxy for C₄ relative abundance, and this variable explained a large proportion of the variation in both collagen δ¹³C (68%) and enamel δ¹³C (68%). These figures increased to 78% and 77%, respectively, when differences between kangaroo species were accounted for. Vegetation characteristics, such as woodiness and the presence of an open forest canopy, had no effect on collagen or enamel δ¹³C. While there was no relationship between collagen δ¹³C and kangaroo age at death, tooth enamel produced later in life, following weaning, was enriched in ¹³C by 3.5‰ relative to enamel produced prior to weaning. From the observed relationships between seasonal water availability and collagen and enamel δ¹³C, enrichment factors (ε^∗) for collagen-diet and enamel-diet (post-weaning) were estimated to be 5.2‰ ± 0.5 (95% CI) and 11.7‰ ± 0.6 (95% CI), respectively. The findings of this study confirm that at a continental scale, collagen and enamel δ¹³C of a group of large herbivores closely reflect C₄ relative abundance. This validates a fundamental assumption underpinning the use of isotopic analysis of herbivore remains to reconstruct changes in C₄ relative abundance.     

Late Holocene Neoglacial conditions from the Lesotho highlands, southern Africa: phytolith and stable carbon isotope evidence from the archaeological site of Likoaeng

The late Holocene environmental history of the Lesotho highlands, southern Africa, is poorly understood with few detailed studies to date. At Likoaeng, Senqu Valley, Lesotho, a 3 m stratified sedimentary sequence from an open-air archaeological site records vegetation development for the period 3400-1070 cal. BP. Phytolith analyses and bulk sediment organic matter δ¹³C indicate that C₄ grassland dominated the lower part of the sequence until approximately 2960 cal. BP when there was a switch to C₃ Pooid grassland (2960-2160 cal. BP). Also noted was a change from hunting mainly bovids to a dominance of fishing at the site. The change in grassland type and archaeological subsistence strategies corresponds with an episode of neoglacial cooling and the expansion of Alpine sourgrasses into lower altitudes. From 2160 to 1600 cal. BP grassland became a mix of C₃ and C₄ types and by 1600-1070 cal. BP there was a return to C₄ dominated grassland. During this latter phase there was a reversal from fishing to hunting again (and eventually some keeping of domestic livestock) at the site. These data outline the vegetation response to latitudinal shifts of frontal systems, and relatively strong atmospheric circulation variability, perhaps underpinned by variations of polar water into the Benguela Current during the late Holocene.     

Stable carbon and oxygen isotope fractionation in bivalve (Placopecten magellanicus) larval aragonite

The relationship between stable isotope composition (δ¹³C and δ¹⁸O) in seawater and in larval shell aragonite of the sea scallop, Placopecten magellanicus, was investigated in a controlled experiment to determine whether isotopes in larval shell aragonite can be used as a reliable proxy for environmental conditions. The linear relationship between δ¹³C_DIC and δ¹³C_aragonite (r² = 0.97, p < 0.0001, RMSE = 0.18) was:

δ¹³C_DIC=1.15(±0.05)∗δ¹³C_aragonite-0.85(±0.04)     

Limitations on the climatic and ecological signals provided by the δC values of phytoliths from a C4 North American prairie grass

Silica phytoliths, which are deposits of opal-A that precipitate in the intra- and intercellular spaces of plant tissues during transpiration, commonly contain small amounts of occluded organic matter. In this paper, we investigate whether the δ¹³C values of phytoliths from a C₄ grass, Calamovilfa longifolia, vary in response to climatic variables that can affect the carbon-isotope composition of plant tissues. There is no significant correlation (r² < 0.3) between climate variables and the δ¹³C values of C. longifolia tissues (average δ¹³C_tissue = −13.1 ± 0.6 ‰; n = 70) across the North American prairies. However, plant tissue δ¹³C values are lower for grasses collected in populated areas where the δ¹³C value of atmospheric CO₂ is expected to be lower because of fossil fuel burning. Phytolith δ¹³C values are more variable (δ¹³C = −27.3 to −23.0‰; average = −25.1 ± 1.3‰; n = 34) and more sensitive to changes in aridity than whole tissue δ¹³C values. The strongest correlations are obtained between the δ¹³C values of stem or sheath phytoliths and humidity (r² = 0.3), latitude (r² = 0.4) and amount of precipitation (r² = 0.5). However, use of these relationships is limited by the wide spread in δ¹³C values of phytoliths from different plant tissues at the same location. We have been unable to infer any relationship between δ¹³C values of phytoliths and expected variations in the δ¹³C values of atmospheric CO₂. The C. longifolia phytoliths are depleted of ¹³C relative to tissue carbon by 10-14‰. This means that the phytoliths examined in this study have carbon isotopic compositions within the range reported previously for phytoliths from C₃ plants. This observation may further limit the usefulness of soil-phytolith assemblage δ¹³C values for identifying shifts in grassland C₃:C₄ ratios.     

Stable carbon isotope behaviour of natural seepage of deep underground C-rich methane detected along a fault zone and adsorbed in mudstone: Tokyo Bay area,Japan

Gas was sampled regionally, including by drilling into faults, in the South Kanto gas-field around Tokyo Bay, Japan. Gas samples were collected from cores in a gas sampling container immediately after drilling. A value of δ¹³C₁ = −44.3‰ was obtained for gas in the container and δ¹³C₁ = −36.3‰ for seeping gas in a fault zone. However, typical CH₄ in this dissolved-in-water gas-field is mainly depleted in ¹³C, and δ¹³C₁ values range from −66‰ to −68‰ owing to microbial degradation of organic material. ¹³C-rich CH₄ is so far uncommon in the South Kanto gas-field. Seepages were observed from the surface along the north–south fault zone. The natural gas is stored below the sandstone layer by impermeable mudstone underlying the boundary at a depth of 30 m. Gas seepages were not observed below a depth of 40 m. Gas rises along the fault zone dissolved-in-groundwater up to the shallow region and then separates from the groundwater. ¹³C-rich CH₄ (adsorbed CH₄) was found to have desorbed from drilled mudstone core samples taken at depths of 1400–1900 m in the main gas-production strata. Similarly, ¹³C-rich CH₄ was found in black shale overlying the oceanic crust forming part of a sedimentary accretionary prism underling the Tokyo region. It also appears in the spring-water of spa wells, originating at a depth of 1200–1500 m along a tectonic line. Methane generated by microbial degradation of organic material through CO₂ reduction in the South Kanto gas-field mainly originates as biogenic gas mixed with a small amount of ¹³C-rich CH₄, derived from thermogenic gas without oil components in strata. It is assumed that ¹²C-rich CH₄ is easily detached from core or pore water through gas production, whereas ¹³C-rich CH₄ is strongly adsorbed on the surfaces of particles. The ¹³C-rich CH₄ rises along the major tectonic line or up the 50 m wide normal fault zone from relatively deep sources in the Kanto region.     

Late Holocene environmental reconstruction using cave sediments from Belize

Cave sediments collected from Reflection Cave on the Vaca Plateau, Belize show variations in the δ¹³C values of their fulvic acids (FAs), which indicate periods of vegetation change caused by climatic and Maya influences during the late Holocene. The δ¹³C values range from − 27.11‰ to − 21.52‰, a shift of ∼ 5.59‰, which suggests fluctuating contributions of C₃ and C₄ plants throughout the last 2.5 ka, with C₄ plant input reflecting periods of Maya agriculture. Maya activity in the study area occurred at different intensities from ∼ 2600 cal yr BP until ∼ 1500 cal yr BP, after which agricultural practices waned as the Maya depopulated the area. These changes in plant assemblages were in response to changes in available water resources, with increased aridity leading to the eventual abandonment of agricultural areas. The Ix Chel archaeological site, located in the study area, is a highland site that would have been among the first agricultural settlements to be affected during periods of aridity. During these periods, minimal water resources would have been available in this highly karstified, well-drained area, and supplemental groundwater extraction would have been difficult due to the extreme depth of the water table.     

The latest Ursus spelaeus in Italy,a new contribution to the extinction chronology of the cave bear

The skeleton of a young prime adult cave bear, Ursus spelaeus, was found in Chiostraccio Cave (Siena, Tuscany, central Italy), only slightly buried under rock falls. The specimen was dated yielding a conventional age of 24,030 ± 100 ¹⁴C yr BP (29,200–28,550 cal yr BP), which makes it the latest known representative of the species in Italy. The skeleton was accompanied by the remains of wolf (Canis lupus), wild boar (Sus scrofa), aurochs (Bos primigenius), red deer (Cervus elaphus), roe deer (Capreolus capreolus), bat (Vespertinus murinus), and crow (Corvus monedula). The site seems confirming that the latest Italian U. spelaeus populations shared the risk of intrusion. The association of the cave bear with other animals suggests that the assemblage is an attritional palimpsest of remains of different species not originally associated in life. Cave bears were probably more vegetarian than brown bears and possibly became extinct when plant productivity dropped at the onset of MIS 2. Central and southern Italy may have offered isolated and sheltered refugia for cave bears.     

C-O bonds in carbonate minerals: A new kind of paleothermometer

The abundance of the doubly substituted CO₂ isotopologue, ¹³C¹⁸O¹⁶O, in CO₂ produced by phosphoric acid digestion of synthetic, inorganic calcite and natural, biogenic aragonite is proportional to the concentration of ¹³C-¹⁸O bonds in reactant carbonate, and the concentration of these bonds is a function of the temperature of carbonate growth. This proportionality can be described between 1 and 50 °C by the function: Δ₄₇ = 0.0592 · 10⁶ · T⁻² − 0.02, where Δ₄₇ is the enrichment, in per mil, of ¹³C¹⁸O¹⁶O in CO₂ relative to the amount expected for a stochastic (random) distribution of isotopes among all CO₂ isotopologues, and T is the temperature in Kelvin. This relationship can be used for a new kind of carbonate paleothermometry, where the temperature-dependent property of interest is the state of ordering of ¹³C and ¹⁸O in the carbonate lattice (i.e., bound together vs. separated into different CO₃²⁻ units), and not the bulk δ¹⁸O or δ¹³C values. Current analytical methods limit precision of this thermometer to ca. ± 2 °C, 1σ. A key feature of this thermometer is that it is thermodynamically based, like the traditional carbonate-water paleothermometer, and so is suitable for interpolation and even modest extrapolation, yet is rigorously independent of the δ¹⁸O of water and δ¹³C of DIC from which carbonate grew. Thus, this technique can be applied to parts of the geological record where the stable isotope compositions of waters are unknown. Moreover, simultaneous determinations of Δ₄₇ and δ¹⁸O for carbonates will constrain the δ¹⁸O of water from which they grew.     

Stable isotope geochemistry of ground and surface waters associated with undisturbed massive sulfide deposits; constraints on origin of waters and water-rock reactions

Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ¹⁸O_VSMOW and δ²H_VSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ¹⁸O_VSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ¹⁸O_VSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ¹³C_VPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO₂ and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ¹³C_VPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ¹³C_VPDB), indicating carbon isotopic fractionation from methanogenesis via CO₂ reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH₄-degassing during sampling.