Oxygen Isotope Values Research Articles

Utilization of stable isotopes in teeth to investigate pygmy sperm whales (Kogia breviceps) in the southeastern United States

AbstractThe pygmy sperm whale (Kogia breviceps) is currently the second‐most stranded cetacean in the southeastern United States (SEUS), but information concerning their population structure is severely limited. This study used stable isotope analysis to investigate the isotopic niches and population structure of K. breviceps among three regions in the SEUS determined by the distance of the continental shelf break and a fourth region in the Gulf of Mexico. Teeth from stranded individuals were subsampled via dental drill at four separate areas on each tooth, representing four different age classes: calf, juvenile, subadult, and adult. Stable isotope ratios of carbon and nitrogen were measured in the organic component of 42 teeth, and oxygen isotope ratios were measured in the inorganic (hydroxyapatite) component of 19 teeth. No differences were found in δ13C, δ15N, or δ18O values between regions. However, differences between age classes were significant for adults and subadults for δ13C and adults and juveniles for δ15N. Differences between males and females were also significant for δ15N. Results from this study provide the first carbon and nitrogen isotope values from different age classes of pygmy sperm whales as well as the first reported oxygen isotope values for this species.

Highly enriched carbon and oxygen isotopes in carbonate-derived CO2 at Gale crater, Mars

Carbonate minerals are of particular interest in paleoenvironmental research as they are an integral part of the carbon and water cycles, both of which are relevant to habitability. Given that these cycles are less constrained on Mars than they are on Earth, the identification of carbonates has been a point of emphasis for rover missions. Here, we present carbon (δ13C) and oxygen (δ18O) isotope data from four carbonates encountered by the Curiosity rover within the Gale crater. The carbon isotope values range from 72 ± 2‰ to 110 ± 3‰ Vienna Pee Dee Belemnite while the oxygen isotope values span from 59 ± 4‰ to 91 ± 4‰ Vienna Standard Mean Ocean Water (1 SE uncertainties). Notably, these values are isotopically heavy (13C- and 18O-enriched) relative to nearly every other Martian material. The extreme isotopic difference between the carbonates and other carbon- and oxygen-rich reservoirs on Mars cannot be reconciled by standard equilibrium carbonate-CO2 fractionation, thus requiring an alternative process during or prior to carbonate formation. This paper explores two processes capable of contributing to the isotopic enrichments: 1) evaporative-driven Rayleigh distillation and 2) kinetic isotope effects related to cryogenic precipitation. In isolation, each process cannot reproduce the observed carbonate isotope values; however, a combination of these processes represents the most likely source for the extreme isotopic enrichments.

Occurrence characteristics of authigenic pyrite in the deep-sea environment and its paleoceanographic implications based on core sediments from IODP Expedition 342 Site U1406

Although authigenic pyrite (FeS2) in marine sediment is an important proxy for oxygen conditions and microbial activities at its formation site, very little is known about its morphological characteristics in the deep-sea (> 3500 m) environment and their paleoceanographic implications. Here, we report the occurrence characteristics of authigenic pyrite including texture, size distribution, and relative content in North Atlantic deep-sea sediments from Integrated Ocean Drilling Program (IODP) Expedition 342 Site U1406. The results of electron microscopy show octahedral pyrite microcrystals of 1.5–4.0 μm, the spherical texture of greigite (Fe3S4), and large pyrite framboids (average, 25 μm) relative to those of the continental margin. These features may demonstrate an unchanged supersaturation level of the pore water for octahedral pyrite after its initial formation, replacement of the precursor greigite by pyrite, and an expanded pyrite framboid formation zone with a low sulfate reduction rate in deep-sea sediments, respectively. Although the size distribution of pyrite framboids measured in this study falls into the range of pyrites formed in the sulfate–methane transition zone, based on onboard geochemical data and previous research, these pyrites most likely formed through organoclastic sulfate reduction during diagenesis. We assessed the implications of these findings for paleoceanographic changes, as the formation of diagenetic pyrite is controlled by the supply rate and reactivity of organic matter, which are closely related to ocean productivity and circulation. A comparison between the profiles of relative pyrite content and benthic foraminiferal oxygen isotope (δ18Obf) values indicated that these factors were anti-phased during the late Oligocene. Based on our results, we conclude that the formation of diagenetic pyrite was favored during interglacial periods due to increases in the amount and reactivity of organic matter driven by more energetic formation of proto-North Atlantic Deep Water. Our findings provide new insights into the formation of authigenic pyrite in deep-sea environments and its potential as a paleoceanographic proxy.

IN SITU STABLE ISOTOPE MEASUREMENTS IN FORAMINIFERAL TESTS BY SIMS

ABSTRACT Fossilized tests of foraminifera are arguably the most important archives of past climate, and many of the longest paleoclimate records have been compiled by the measurement of the oxygen and carbon isotope composition of foraminiferal tests collected from seafloor sediments. Since the analytical methodology was established in the late 1940s, multiple tests are pooled and analyzed, resulting in a single oxygen and carbon isotope value representing their mean composition. These records compiled by multi-test analysis provide, in most scenarios, a faithful picture of the Earth’s past climate. However, foraminiferal tests feature isotopic heterogeneity on micrometer scales and thus record a wealth of additional information that can be assessed by secondary ion mass spectrometry (SIMS) using spots of 10 µm or less. This paper provides a history of in situ stable isotope measurements in foraminifer tests by SIMS, discusses landmark studies, and offers an outlook on future research.

Timing and origin of the Lomagundi-Jatuli Event: Insights from U[sbnd]Pb geochronology, C-O-Fe isotopes and REE compositions from the Jingshan Group, North China Craton

The Lomagundi-Jatuli Event (LJE) represents perhaps the largest and longest positive carbon isotope excursion of Earth history. However, the synchroneity, scale, and linkage of the LJE to Earth's early history of atmospheric oxygenation remain controversial. Strata of the Paleoproterozoic Jingshan Group of the North China Craton that preserve the isotopic record of the LJE excursion in marble layers and abundant graphite deposits provide an opportunity to elucidate the significance of the LJE. Carbon isotopic values (δ13CV-PDB) of the LJE based on analysis of 20 samples of the Lugezhuang Formation, lower Jingshan Group, range from −0.8 to +9.6 ‰ and display positive co-variance with stable oxygen isotope values (δ18OV-PDB). The positive carbon isotope excursion is constrained to 2140.6 ± 8.5 Ma (MSWD = 0.82, n = 25) based on magmatic zircon UPb geochronology of biotite granulite. Variation of facies-dependent carbon isotope values, the presence of graphite deposits of the Douya Formation, upper Jingshan Group, and the absence of a Ce anomaly in PAAS normalized REE patterns of marble samples suggest that the positive carbon isotope excursion is not linked to a marked increase of organic carbon burial and associated significant atmosphere oxygenation. Elevated concentrations of iron and PAAS-normalized middle REE enrichment of analyzed Jingshan Group marble samples point to anoxic and ferruginous oceanic conditions during accumulation of Jingshan Group carbonate. A positive Eu anomaly (average = 1.58), low La (average = 0.23), (Nd/Yb)N (average = 1.27), and Y/Ho (average = 36.6) anomalies, and negative iron isotope values (average δ56Fe = −0.12 ‰) are consistent with accumulation of Paleoproterozoic Jingshan Group carbonate in a restricted marine setting that was affected by high temperature hydrothermal fluids. Enrichment of the studied samples in heavy carbon isotope suggests elevated bio-productivity in the restricted, redox stratified marine setting in which Jingshan Group carbonate accumulated. Thus, it is likely that the positive stable carbon isotope excursion associated with Jingshan Group strata as well as other contemporaneous isotope excursions are local signals that are linked to a global perturbation of the carbon cycle.

Isotope values reveal “canopy effect” in deer territoriality and maize consumption for dogs from archaeological sites in Kentucky dating to the Middle Woodland through Late Fort Ancient time periods

This research analyzes stable carbon, nitrogen, and oxygen isotope values in tooth collagen and enamel to investigate foraging and territorial behavior in white-tailed deer (Odocoileus virginianus Zimmermann) and maize (Zea mays Linneaus) consumption in dogs (Canis familiaris Linneaus). The study analyzed 22 deer teeth from 13 archaeological sites in Kentucky covering a span of approximately 1,500 years of human occupation. The article presents evidence of foraging and territorial behavior in white-tailed deer, identified through the “canopy effect” observed in deer stable carbon isotope values in remains spanning from the Middle Woodland (200 BCE – CE 500) to Late Fort Ancient (CE 1400 – 1680) time periods in Kentucky. Additionally, teeth samples from nine dog and one wolf (Canis lupus Linneaus) were analyzed and indicate significant consumption of maize in seven of the dog samples. These specimens came from seven archaeological sites in Kentucky dating from the Early through Late Fort Ancient (CE 1400 – 1680) time periods. The study also contributes to the growing database of isotope studies in the Eastern Woodlands by presenting carbon and nitrogen isotope values on deer bone collagen from nine deer bone samples from three of the same archaeological sites dating to the Middle Woodland to Early Late Woodland.

Taxonomic and stable isotope analyses of mammal remains from the Lateglacial site of Grotta Polesini (central Italy): Paleoenviromental implications

ABSTRACTGrotta Polesini is one of the most famous paleontological and archaeological sites of central Italy, which testifies to its human occupation during the Lateglacial. The site comprises a cave system where systematic excavation campaigns have been carried out since the 1950s. In 1974, 656 mammal remains were collected but never studied. This fossil collection is here described for the first time through taxonomic and stable isotope analyses of the enamel of selected mammal teeth. The aim is to reconstruct the paleoenvironmental and climatic conditions of the site and to offer new information on terrestrial ecosystems during the Lateglacial in central Italy. The faunal assemblage studied herein, in addition to other species reported in previous works, suggests cold climate conditions. We also describe a right radius of an adult individual of Homo sapiens, increasing the human fossil record of the site. Carbon isotope data point to a scenario dominated by C3 plants in open and dry habitats, such as grasslands and steppes, in accordance with the pollen data from central Italy. The oxygen isotope data suggest the use of water resources with a local origin, i.e. local precipitation and surface waters with a provenance from the nearby Apennine chain. The ecology of the taxa influenced the oxygen isotope values, especially in the case of semi‐obligate to non‐obligate drinker species.

The formation of tubular seep carbonate deciphered from mineralogical and geochemical characteristics: an example from the South China Sea

As a special type of seep carbonate, the many details concerning the formation mode and mechanism of tubular seep carbonates are rarely reported. Here, new geochemical and mineralogical data regarding tubular seep carbonate (SQW-65) are reported. Sample SQW-65 had anomalously negative δ13C values and positive δ18O values, which suggested the dissociation of gas hydrate. Additionally, almost all the sub-samples showed no Ce anomaly (Ce/Ce*average = 0.93), with obvious U enrichment (21.3< UEF <240.3), which indicates that the studied tubular seep carbonate was formed in an anoxic environment. Subsequently, the formation process of the studied tubular seep carbonate is further discussed according to the variability of mineralogical and geochemical characteristics from the rim to the core of the tubular formation. In the early stage of the studied tubular seep carbonate (periphery), owing to the influence of terrigenous components, the quartz and Ti content and Y/Ho ratio were high. However, with the formation of the periphery, the influence of terrigenous components was gradually weakened. In addition, from the rim to the core, the carbon and oxygen isotope values showed a “covariation” coupling relationship, an enrichment of U, and a reduction in total rare earth element content. This is because as the outer wall thickens and the internal fluid channel narrows, the intensity of the sulphate-driven anaerobic oxidation of methane and the associated precipitation rate of carbonate also increase.

Position-Specific Oxygen Isotope Analysis in Inositol Phosphates by Using Electrospray Ionization-Quadrupole-Orbitrap Mass Spectrometry.

Conventional isotope-ratio mass spectrometry measurements obscure position-specific isotope distributions in molecular compounds because these measurements require an initial step that converts compounds into simple gases by combustion or pyrolysis. Here, we used electrospray ionization (ESI)-based Orbitrap mass spectrometry to measure oxygen isotope ratios in the phosphate and hydroxyl moieties of inositol phosphates. A thermal hydrolysis experiment was conducted using 18O-labeled water to examine the position-specific oxygen isotope exchange in inositol hexakisphosphate (IP6) as well as its hydrolysis products IP5, IP3, and PO3 fragments. Measurement precisions of the position-specific and molecular-average oxygen isotope values of inositol phosphates were better than ±1.1‰ and ±0.5‰, respectively. Under optimized ionization and Orbitrap parameters, this level of precision was obtained within 30 min of run time at 60 μM initial concentration of inositol phosphate. The ability to measure phosphate-specific oxygen isotopes in inositol phosphate enabled the quantification of isotope exchange, which did not occur in phosphate on IP6, IP5, IP3, and PO3 fragments, meaning that the change in isotopes should have resulted from hydroxyls in the ring. Isotope mass balance calculations corroborated that hydroxyl oxygens are derived from 18O-labeled water. With the observed sensitivity and precision achieved in this study, Orbitrap IRMS proved to be a promising tool for investigating the position-specific oxygen isotopes in organophosphorus compounds. These outcomes open up numerous potential applications that can expand our understanding of phosphorus cycling in the environment.

Reservoir heterogeneities due to diagenesis in Jurassic Samana Suk Formation Kahi section Nizampur Basin North West Himalayas Pakistan

The porosity and permeability determine the reservoir quality of sedimentary rocks, which is fundamentally influenced by both depositional and diagenetic processes. The Jurassic carbonates are targeted in many regions for oil and gas exploration. The current study is carried out to elaborate on the diagenetic alterations and their effect on reservoir properties. A thick outcrop of the Jurassic Samana Suk Formation is studied in the Kahi section of Nizampur Basin Northwest Himalayas, Pakistan, to study and relate the trend of lithological variations and depositional settings. Field investigation revealed that the Samana Suk Formation is extensively distributed in the area and primarily made up of interbedded limestone and dolomite units. The original unaltered limestone has a thick-bedded and oolitic to bioclastic nature. Different types of dolomites have been recognized based on colour contrast and sedimentary features. Moreover, saddle dolomite cement, calcite cementation, and mechanical and chemical compaction have also been observed. The petrographic studies show different types of diagenetic alterations that affected the Samana Suk Formation, including micritization, bioturbation, mechanical and chemical compaction in the form of fractures and stylolites, various calcite cementation, which includes the various cement types that range from isopachous, blocky, granular equant, fibrous, and dog tooth cementation, along with dissolution that occurred in different diagenetic realms. Pyritization was rarely observed. Moreover, different phases of dolomites were identified, ranging in size and shape, i.e., finely crystalline to coarse crystalline and planar euhedral to non-planar anhedral. The stable oxygen isotope values of these dolomites show depletion from original marine signatures and suggest burial-related fault-controlled dolomitization events. Overall, diagenetic processes like dissolution, fracturing and dolomitization increased the reservoir potential. On the contrary, the overburden and cement precipitation result in a decrease in the reservoir properties.

Mytilus galloprovincialis shell growth – Insights from shell geochemistry

Despite the wide geographic distribution of mussels and their importance in fisheries and aquaculture, understanding of temporal and spatial variations of their growth is still limited. This can be, at least partly, attributed to the lack of distinct growth lines in their shells. Our study uses geochemical properties of shells, particularly oxygen (δ18Oshell) and carbon (δ13Cshell) stable isotope values, to reconstruct mussel growth. Mytilus galloprovincialis specimens were collected from two of the most important bivalve aquaculture sites in the eastern Adriatic - Krka River estuary and Mali Ston Bay. The first site has variable environmental conditions, influenced mainly by the Krka River, resulting in a strong temperature and salinity gradient along the estuary. In contrast, Mali Ston Bay is a relatively shallow enclosed bay with more stable conditions. Samples for δ18Oshell and δ13Cshell analysis were acquired by manual microdrilling cross-sectioned shells from three similar sized shells from each site. In addition, analysis of elemental profiles (Mg/Ca, Sr/Ca, and Ba/Ca) in shells from the Krka River estuary was conducted using laser ablation ICPMS. Temperature and salinity values were obtained for each site through research and monitoring projects and used to calculate predicted δ18Oshell values. By aligning the measured δ18Oshell data along the predicted δ18Oshell curve, it was possible to reconstruct the timing and rate of seasonal shell growth. Results show that M. galloprovincialis shell deposition slows down and/or ceases during high temperature and low salinity periods. Specimens from the Krka River estuary had faster shell growth rates and were characterised by higher δ13Cshell values. Mg/Ca profiles of M. galloprovincialis specimens from the Krka River estuary, confirm growth periodicity data obtained by δ18O analysis. Ba/Ca peaks were also discussed by comparison with δ13C time-series and environmental data. Results have potential applications in fisheries studies as well as in palaeoecology and palaeoceanography research.

The Characteristics and Application of Deuterium and Oxygen Isotopes to Karst Groundwater, Southwest China

Stable isotopes in natural water bodies serve as hydrologic tracers, with a history of extensive application in karst groundwater research. The present paper is a systematic review of previous research results, with the objective of sorting out and summarizing the stable isotopic characteristics of karst groundwater in southwest China, which is the most typical karst region worldwide. Comprehensive analysis reveals that the deuterium and oxygen isotope values of most karst groundwater are characterized temporally as ‘enriched in the rainy season and depleted in the dry season’, which is the opposite of the pattern of precipitation. While the spatial distribution feature is basically consistent with the spatial variation pattern of precipitation, which is characterized as ‘depleted from the coast to the interior’. Additionally, the main applications of stable isotopes to karst groundwater are discussed, including karst groundwater recharge source and recharge elevation identification, research on karst groundwater in the hydrological cycle, the hydrological process of karst groundwater, and karst groundwater contamination tracking. Finally, we looked forward to future research on karst groundwater based on deuterium and oxygen isotopes. It is our hope that this review may provide insight into the study of karst groundwater.

Aquatic moss δ18O as a proxy for seasonally resolved lake water δ18O, northwest Greenland

Reconstructing past climate seasonality is fundamental to understanding the nature of past climate changes. This is especially true in the Arctic, where climate is intensely seasonal and proxies that can distinguish climate conditions of multiple seasons in a single year are relatively rare. We propose that submerged aquatic mosses, which are abundant subfossils in some Arctic lake sediments and have distinctive seasonal growth morphologies, can be used to estimate past lake water oxygen isotope composition (δ18Olw) across multiple seasons. Aquatic mosses are abundant, well preserved, and grow continuously in Arctic lakes whenever light is available, with some species displaying unique seasonal morphologies influenced by water temperature. Although Greenland paleorecords suggest that aquatic moss oxygen isotope values (δ18Oom) reflect the δ18O values of lake water, no modern calibration between δ18Oom and δ18Olw exists in Greenland. We present a modern δ18Oom vs. δ18Olw calibration using multiple moss species or morphotypes from eight lakes and ponds near Pituffik (Thule), northwest Greenland. We find strong linear relationships (r2 = 0.76-0.85) between the δ18Oom and δ18Olw values of multiple species or morphotypes across the range of relatively low δ18Olw values at Pituffik, and our results indicate isotopic fractionations are similar to those found previously at lower latitudes. To assess the potential of mosses as archives of seasonal δ18Olw values, we analyzed δ18Oom in season-specific segments of moss strands, with seasons identified based upon growth morphology. Moss inferred lake water δ18O values (δ18Olwom) are higher in autumn than spring or summer, likely due to increasing contributions of 18O enriched precipitation and the cumulative effects of lake water evaporation throughout the ice-free season. For moss subsampled throughout summer, δ18Olwom values generally increased through the season in parallel with observed δ18Olw values. Potential temperature dependent fractionation effects during biosynthesis, however, remain unconstrained and should be further addressed with future research. Overall, these findings suggest that aquatic mosses from lake sediments could be used to directly resolve climate seasonality of the past.

Late Holocene climate dynamics in the Azores archipelago

The location of the Azores Archipelago makes this group of islands an excellent setting for investigating past long-term temperature and precipitation changes in the central North Atlantic region. Here, we present a chironomid-based quantitative temperature reconstruction and a record of oxygen isotope composition of chironomid head capsules for the last ca. 1200 years, based on the Lake Prata core (São Miguel Island, Azores). Chironomids from Lake Prata show that the temperature trend is aligned with the prevailing past global temperature trends, indicating warming during the Medieval Climate Anomaly (MCA; ca. 950–1300 CE) and subsequent cooling during the Little Ice Age (LIA; ca. 1300–1800 CE). Furthermore, changes in lake water oxygen isotope composition from chironomid head capsules were recorded with more positive δ18O values (18.2 ± 0.2‰) during the MCA and more negative values (varying between 14.8‰ and 17.6‰) during the LIA, indicating a positive shift in the precipitation-evaporation balance and/or heavier precipitation in winter relative to summer. Our study revealed that, in subtropical regions with a temperate oceanic climate and low thermal variation, there is a limited correlation between the isotopic composition of precipitation and temperature. Additionally, the temporal sequence of oxygen isotope values obtained from chironomid head capsules closely corresponds to variations in precipitation seasonality inferred from distinct climatic proxies. This consistency underscores the robustness of quantitative reconstructions and indicates that δ18Ochironomid records are promising for future investigations, especially in the context of lakes located on oceanic islands characterised by limited thermal variability.

The competitive relationship of scrub plants for water use in the subalpine zone of the Qilian Mountains in China.

Samples of scrub plants and soil were collected from May to October 2019 in the subalpine scrub zone of the Qilian Mountains. Based on measured oxygen isotope values (δ18O) in plant xylem water and soil water, the multivariate linear mixed model (IsoSource) and the proportional similarity index (PS index) were used to analyze the using proportion for each potential water source and the competition relationship for water use of scrub plants in different growing periods and habitats. The results showed that the soil water content gradually decreased with increasing depth of the soil layer, with the maximum value in the soil layer of 0-10cm. Most of the scrub plants mainly used soil water in the soil layer of 0-30cm during the different periods of growing season, but Salix sclerophylla Anderss. and Salix oritrepha Schneid. on the semi-sunny slope habitat mainly used soil water in the soil layer of 40-80cm during the middle period of growing season (July-August), with the proportion of 59.5% and 52.1%, respectively; and Potentilla fruticosa Linn. and Salix cupularis Rehd. on the semi-shady slope habitat mainly used soil water in the soil layer of 30-60cm during the early period of growing season (May-June), with the proportion of 61.1% and 49.7%, respectively. The competition relationships of scrub plants for water use varied during different periods of growing season (P < 0.05). On the semi-sunny slope habitat, they were fiercest for Salix cupularis Rehd. and Rhododendron thymifolium Maxim., Potentilla fruticosa Linn., and Salix sclerophylla Anderss. during the early period of growing season; Salix cupularis Rehd. and Rhododendron thymifolium Maxim. during the middle period of growing season, and Salix sclerophylla Anderss. and Salix oritrepha Schneid. during the end period of growing season (September-October). On the semi-shady slope habitat, they were fiercest for Salix oritrepha Schneid. and Caragana jubata (Pall.) Poir. during the early period of growing season; Rhododendron przewalskii Maxim. and Rhododendron thymifolium Maxim. during the middle period of growing season; and Salix cupularis Rehd. and Salix oritrepha Schneid. during the end period of growing season. This study reveals the competitive relationship of scrub plants for water use in the subalpine zone and their response to environmental changes, so as to provide theoretical references for the ecological conservation in the ecologically fragile areas of the Qilian Mountains.

Vittrup Man-The life-history of a genetic foreigner in Neolithic Denmark.

The lethally maltreated body of Vittrup Man was deposited in a Danish bog, probably as part of a ritualised sacrifice. It happened between c. 3300 and 3100 cal years BC, i.e., during the period of the local farming-based Funnel Beaker Culture. In terms of skull morphological features, he differs from the majority of the contemporaneous farmers found in Denmark, and associates with hunter-gatherers, who inhabited Scandinavia during the previous millennia. His skeletal remains were selected for transdisciplinary analysis to reveal his life-history in terms of a population historical perspective. We report the combined results of an integrated set of genetic, isotopic, physical anthropological and archaeological analytical approaches. Strontium signature suggests a foreign birthplace that could be in Norway or Sweden. In addition, enamel oxygen isotope values indicate that as a child he lived in a colder climate, i.e., to the north of the regions inhabited by farmers. Genomic data in fact demonstrates that he is closely related to Mesolithic humans known from Norway and Sweden. Moreover, dietary stable isotope analyses on enamel and bone collagen demonstrate a fisher-hunter way of life in his childhood and a diet typical of farmers later on. Such a variable life-history is also reflected by proteomic analysis of hardened organic deposits on his teeth, indicating the consumption of forager food (seal, whale and marine fish) as well as farmer food (sheep/goat). From a dietary isotopic transect of one of his teeth it is shown that his transfer between societies of foragers and farmers took place near to the end of his teenage years.

Marine resource exploitation and human settlement patterns during the Neolithic in SW Europe: stable oxygen isotope analyses (δ18O) on Phorcus lineatus (da Costa, 1778) from Campo de Hockey (San Fernando, Cádiz, Spain)

In recent decades, investigations in the southern Iberian Peninsula have increased our understanding of the socio-economic impact of the spread of the Neolithic in southwestern Europe, including changes in marine resources exploitation. Nevertheless, considerable uncertainty still exists around the seasonality of such subsistence systems and the putative role of marine fish and shellfish to the evolving agro-pastoral economies. Earlier studies on the European Atlantic coast (including Iberia) have shown that the stable oxygen isotope (δ18O) values from the topshell Phorcus lineatus (da Costa, 1778) can be reliably used to derive seasonal sea surface temperatures (SST) during its lifespan. This information can be used by archaeologists to estimate the seasonality of mollusc collection in the past, and to shed light into settlement and subsistence patterns. This paper presents the results of a stable isotope study on archaeological shells of P. lineatus recovered from the Neolithic settlement of Campo de Hockey (Cádiz, Spain). We analysed shells from both funerary and residential contexts and found that P. lineatus was consumed year-round, but with a stronger preference during winter. Our results therefore contribute to advance our understanding of the role of coastal environments in early farming societies of southwestern Europe.

Hydrochemical Characteristics and Its Origin of Surface Water and Groundwater in Dianbu River Basin

Chaohu lake is a key water body for water pollution prevention and treatment in our country. However， it has been at a higher eutrophication level recently. Here， the surface water and groundwater in the Dianbu River Basin， a secondary tributary of Chaohu Lake， were taken as the research object. In order to test the hydrochemical composition and hydrogen and oxygen isotope values of different water bodies， 30 groups of surface water samples， 36 groups of groundwater samples， 16 groups of hydrogen and oxygen stable isotope samples， and 18 groups of groundwater hydrogen and oxygen stable isotope samples were collected in August 2021 （wet season）， November 2021 （normal season）， and February 2022 （dry season）. The seasonal and spatial variation characteristics were analyzed to explore the hydrochemical characteristics and formation mechanism of water bodies by means of mathematical statistics， Piper triangular diagram， Gibbs figures， and ion ratios. The following results were obtained： ① precipitation was the main source of surface water and groundwater in Dianbu River Basin， and the evaporation fractionation effect of surface water was more significant than that of groundwater. At different periods， the surface water was more enriched with stable isotopes of hydrogen and oxygen than groundwater. The stable isotopes of hydrogen and oxygen in water showed seasonal variation， relative enrichment in the wet season， and depletion in the dry season. ② Both surface water and groundwater in the Dianbu River Basin were weakly alkaline， and the concentration of ions in surface water was significantly lower than that in groundwater. Ca2+ and Na+ were the main cations in surface water， Ca2+ was the main cation in groundwater， and the dominant anion in all water was HCO3-. The hydrochemical typology of surface water was mainly HCO3·Cl-Na·Ca， and that of groundwater was mainly HCO3-Na·Ca. ③ The concentrations of the main hydrochemical indexes of surface water and groundwater showed certain seasonal and spatial differences. From the wet season to the dry season， the concentrations of TDS， K+， Na+， Ca2+， Mg2+， Cl-， and SO42- in surface water showed an increasing trend on the whole. The concentrations of Na+， Ca2+， and Mg2+ in groundwater showed little change but increased slightly， whereas the concentrations of Cl-， SO42-， and NO3- showed an increasing trend on the whole. The concentrations of Cl-， SO42-， and NO3- in the water showed relatively large seasonal fluctuations. From upstream to downstream， the concentrations of the main hydrochemical indexes in surface water first decreased and then increased， among which the concentration of NO3- increased the most. The concentrations of the main hydrochemical indexes of groundwater in the direction of runoff changed little overall， but the concentration in the discharge area was higher than that in the recharge area. ④ The formation of hydrochemical characteristics of the water was mainly controlled by water-rock interaction but was also influenced by human factors. The water-rock action was mainly the weathering dissolution of silicate rock， salt rock， and carbonate rock. Man-made pollutants such as sewage from a sewage treatment plant， domestic sewage， and feces had obviously changed the hydrochemical characteristics of the local water. ⑤ Compared with that in 2016， the concentration of NO3- in surface water showed a certain degree of reduction. The nitrogen pollution control work carried out by the local government had achieved certain results， but it was still necessary to strengthen the pollution prevention and control of sewage and feces in the downstream of the Dianbu River， some tributaries （such as the Dingguang River and Maqiao River）， and some residential areas.

Hydrogeochemical and Isotopic Characterisation of the Učja Aquifer, NW Slovenia

The groundwater characteristics of the Učja aquifer were investigated using geochemical and isotopic data. The water discharge and physico-chemical properties of the groundwater and the Učja River reflect the climate that is characteristic of the area. The mixed snow/rainfall regime is characteristic for the Učja Valley, with the highest discharges appearing during the spring snowmelt and autumn precipitation, and the lowest discharges in the winter and especially summer months. The temperature of the groundwater and the Učja River is lower in winter and higher in summer. The specific electrical conductivity values indicate a very permeable carbonate aquifer. Higher conductivity values were observed in spring and autumn at all sampling sites, which is related to snowy and rainy periods. The groundwater from the Učja aquifer indicates a uniform type of water (Ca-Mg-HCO3), with Ca2+, Mg2+ and HCO3– the most abundant ions. Differences in Ca2+ and Mg2+ concentrations and in the Mg2+/Ca2+ molar ratio between sampling sites were observed. Those springs with lower Mg2+ and lower Mg2+/Ca2+ molar ratios indicate limestone recharge areas, and those springs with higher Mg2+ and molar ratios indicate interaction with the dolomite hinterland. The pH values confirm alkaline waters characteristic of carbonate aquifers. The hydrogen (δ2H) and oxygen (δ18O) isotope values suggest the main source of water is from precipitation from a complex mixing of maritime and continental air masses. An altitude isotopic effect is observed with minor δ18O and δ2H depletion at higher altitude sampling sites compared to those springs at lower altitudes. The altitude isotopic effect is most prominent in spring. The δ13CDIC values indicate the dissolution of carbonates and the degradation of organic matter.

Determining of an oceanic anoxic event and paleoenvironmental conditions of the Gulneri Formation Kirkuk Oilfield, Northern Iraq

Stable isotopic geochemistry in relation to major and trace elements geochemistry of core samples from the Gulneri Formation at Kirkuk Oilfield Northern Iraq has been conducted to determine the occurrence of the oceanic anoxic event (OAE2) and reconstruct the paleoenvironmental conditions during this event. Positive values of the stable carbon isotopic data have revealed that temperature is high during deposition accompanied with higher organic productivity and a high rate of organic carbon burial with a decrease in dissolved oxygen in marine environments, whereas, negative oxygen isotopic values indicate deposition in hot, dry, semi-arid environments with salty marine waters and high organic productivity. These results were also supported by geochemical evidence of paleoclimate through C-value and ratios of Sr/Cu, Rb/Sr, and Ga/Rb, paleosalinity using proxies from Ca/Ca+Fe and Sr/Ba ratios, and paleoproductivity using P/Ti, P/Al and barium ratios. The paleoredox proxies from V/(V+Ni), V/Ni, and U/Th ratios and Uδ indicate dominant anoxic conditions. The recorded oceanic anoxic event (OAE2) has been determined through significant excursion in carbon and oxygen isotopic values as well as geochemical proxies within the sequences of the upper part of the formation marking the final stage of the OAE event.