Abiotic aerobic oxidation pathways of stibnite revealed by oxygen and sulfur isotope systematics of sulfate.

The environmental threat posed by stibnite is an important geoenvironmental issue of current concern. To better understand stibnite oxidation pathways, aerobic abiotic batch experiments were conducted in aqueous solution with varying δ18OH2O value at initial neutral pH for different lengths of time (15-300 days). The sulfate oxygen and sulfur isotope compositions as well as concentrations of sulfur and antimony species were determined. The sulfur isotope fractionation factor (Δ34SSO4-stibnite) values decreased from 0.8‰ to -2.1‰ during the first 90 days, and increased to 2.6‰ at the 180 days, indicating the dominated intermediate sulfur species such as S2O32-, S0, and H2S (g) involved in Sb2S3 oxidation processes. The incorporation of O into sulfate derived from O2 (∼100%) indicated that the dissociated O2 was only directly adsorbed on the stibnite-S sites in the initial stage (0-90 days). The proportion of O incorporation into sulfate from water (27%-52%) increased in the late stage (90-300 days), which suggested the oxidation mechanism changed to hydroxyl attack on stibnite-S sites promoted by nearby adsorbed O2 on stibnite-Sb sites. The exchange of oxygen between sulfite and water may also contributed to the increase of water derived O into SO42-. The new insight of stibnite oxidation pathway contributes to the understanding of sulfide oxidation mechanism and helps to interpret field data.

Enhancing hydrological insight: isotopic methods revealing groundwater-surface water interactions in the Lower Quang Tri River Group, Vietnam.

The Lower Quang Tri River Group, situated in central Vietnam, faces a myriad of challenges, notably the decline in groundwater levels and the salinisation of both groundwater and surface water, significantly impacting water availability for domestic, agricultural, and industrial purposes. To address these pressing concerns, this study adopts a comprehensive methodology integrating hydrogeological measurements, isotopic techniques, and chemical analyses of various water sources, including local precipitation, surface water bodies, reservoirs, and groundwater samples. Utilising the deuterium and oxygen-18 signatures (δ2H and δ18O) in water molecules as environmental tracers for the assessment of base flow and water sources enables a nuanced understanding of the intricate interaction between surface water and groundwater. Research findings elucidate that during the dry season, groundwater recharge primarily stems from water in the reservoirs over approximately seven months. Base flow contributes between 80 and 85 % of streamflow during the rainy season, escalating to 100 % during the dry season. The mean travelling time of the base flow is estimated at 120 ± 10 days using the sine curve model developed by Rodgers et al. The insights gleaned from this study are poised to play a pivotal role in guiding the local water resources managers in licensing for the exploitation of a right quantities of groundwater as sustainable management strategies in the region.

Estimates of late Early Cretaceous atmospheric CO2 from Mongolia based on stomatal and isotopic analysis of Pseudotorellia.

PREMISE: The Aptian-Albian (121.4-100.5 Ma) was a greenhouse period with global temperatures estimated as 10-15°C warmer than pre-industrial conditions, so it is surprising that the most reliable CO2 estimates from this time are <1400 ppm. This low CO2 during a warm period implies a very high Earth-system sensitivity in the range of 6 to 9°C per CO2 doubling between the Aptian-Albian and today. METHODS: We applied a well-vetted paleo-CO2 proxy based on leaf gas-exchange principles (Franks model) to two Pseudotorellia species from three stratigraphically similar samples at the Tevshiin Govi lignite mine in central Mongolia (~119.7-100.5 Ma). RESULTS: Our median estimated CO2 concentration from the three respective samples was 2132, 2405, and 2770 ppm. The primary reason for the high estimated CO2 but with relatively large uncertainties is the very low stomatal density in both species, where small variations propagate to large changes in estimated CO2. Indeed, we found that at least 15 leaves are required before the aggregate estimated CO2 approaches that of the full data set. CONCLUSIONS: Our three CO2 estimates all exceeded 2000 ppm, translating to an Earth-system sensitivity (~3-5°C/CO2 doubling) that is more in keeping with the current understanding of the long-term climate system. Because of our large sample size, the directly measured inputs did not contribute much to the overall uncertainty in estimated CO2; instead, the inferred inputs were responsible for most of the overall uncertainty and thus should be scrutinized for their value choices.

Triple-isotope analysis in tree-ring cellulose suggests only moderate effects of tree species mixture on the climate sensitivity of silver fir and Douglas-fir.

Disentangling the factors influencing the climate sensitivity of trees is crucial to understanding the susceptibility of forests to climate change. Reducing tree-to-tree competition and mixing tree species are two strategies often promoted to reduce the drought sensitivity of trees, but it is unclear how effective these measures are in different ecosystems. Here, we studied the growth and physiological responses to climate and severe droughts of silver fir and Douglas-fir growing in pure and mixed conditions at three sites in Switzerland. We used tree-ring width data and carbon (δ13C), oxygen (δ18O) and hydrogen (δ2H) stable isotope ratios from tree-ring cellulose to gain novel information on water relations and the physiology of trees in response to drought and how tree species mixture and competition modulate these responses. We found significant differences in isotope ratios between trees growing in pure and mixed conditions for the two species, although these differences varied between sites, e.g. trees growing in mixed conditions had higher δ13C values and tree-ring width than trees growing in pure conditions for two of the sites. For both species, differences between trees in pure and mixed conditions regarding their sensitivity to temperature, precipitation, climatic water balance and vapor pressure deficit were minor. Furthermore, trees growing in pure and mixed conditions showed similar responses of tree-ring width and isotope ratios to the past severe droughts of 2003, 2015 and 2018. Competition had only a significantly negative effect on δ13C of silver fir, which may suggest a decrease in photosynthesis due to higher competition for light and nutrients. Our study highlights that tree species mixture may have only moderate effects on the radial growth and physiological responses of silver fir and Douglas-fir to climatic conditions and that site condition effects may dominate over mixture effects.

North and South in Medieval Iberia: A historical and environmental estimate through isotopic analyses.

The Middle Ages in the Iberian Peninsula is a period of special interest for studying the relationship of climate change with historical and socioeconomic processes. Between the 8th and 15th centuries AD, the Peninsula was characterized not only by complex political, cultural, and social transitions but also by major variations in the climate. The objective of this study was to examine differences in diet and mobility between distinct populations of the Peninsula and explore the possible relationship of diet, mobility, and culture with environmental variables and geographical settings. For this purpose, we obtained stable isotopic ratios of carbon and oxygen (δ13C and δ18O) from the enamel apatite of first upper incisors from 145 individuals at eight archeological sites that represent both Christian and Islamic communities and both rural and urban social settings. Results revealed a dietary difference between Christian and Islamic populations, observing a greater contribution of C4 plants, possibly sorghum, in the diet of the latter, especially in a rural setting. The disparity in oxygen isotopic ratios between populations from the North and South of the Peninsula is consistent with modern climatic differences between these regions. In this line, intraregional variability in oxygen isotopic ratios may hint at diachronic occupation phases under varying climatic conditions. The few isotopic outliers in our sample suggest overall low mobility levels.

[Characterization of carbon and oxygen isotopes of plant on climate and plant physiology at the southeastern margin of Qinghai-Tibet Plateau, China]. / é’è—é«˜åŽŸä¸œå—ç¼˜æ¤ç‰©ç¢³æ°§åŒä½ç´ å¯¹æ°”å€™åŠæ¤ç‰©ç”Ÿç†çš„è¡¨å¾.

To investigate the correlation between carbon and oxygen isotope compositions of plant cellulose and climatic factors as well as plant physiological indices on the southeastern margin of the Qinghai-Tibet Plateau, we examined plant species in eight sampling sites with similar latitudes and different longitudes in this region. Through the characteristics of δ13C and δ18O values, fractionation values (Δ13C and Δ18O) in leaf cellulose, we discussed water use efficiency (WUE) and the environmental factors, the variation of carbon and oxygen isotopes in the southeastern margin of the Qinghai-Tibet Plateau with elevation and longitude, and revealed the indication degrees of isotopic signals to different environments and vegetation physiology. By using the semi-quantitative model of carbon and oxygen dual isotopes, we investigated the physiological adaptation mechanisms of plants to varying environmental conditions. The results demonstrated that both Δ13C and Δ18O of cellulose decreased with increasing elevation and longitude, and Δ13C was more influenced by longitude, while Δ18O was more susceptible to elevation variation. Additionally, Δ13C and Δ18O were significantly and positively correlated with temperature (TEM), precipitation (PRE), potential evapotranspiration (PET), and relative humidity (RH). PRE was the dominant meteorological factor driving the variation of Δ13C, while RH was the dominant meteorological factor influencing Δ18O variation. In contrast to Δ13C, WUE showed a stronger correlation with elevation than with longitude, which increased as elevation and longitude increased. According to the carbon-oxygen model, plant stomatal conductance (gs) and photosynthetic capacity (Amax) decreased with increasing precipitation and relative humidity, while the values increased with increasing elevation and longitude. The combined analysis of carbon and oxygen isotopes of organic matters would yield additional environmental and gas exchange information for studies on climate tracing and vegetation physiology studies on the southeastern margin of the Qinghai-Tibet Plateau.

[Temporal variability of the isotope compositions of plum rain in Nanjing from event to interannual time scales]. / å—äº¬æ¢ é›¨é™æ°´åŒä½ç´ ç»„æˆä»Žäº‹ä»¶åˆ°å¹´é™ å°ºåº¦çš„å˜åŒ–ç‰¹å¾.

Precipitation in the plum rain period accounts for 40%-50% of annual precipitation in the monsoon region. To clarify the temporal variability of the isotopic composition of precipitation during the plum rain period from event to interannual time scale and identify the influencing factors, we analyzed the isotopic composition of precipitation and its influencing factors in Nanjing from 2015 to 2022. By using the Hybrid Single-particle Lagran-gian Integrated Trajectory (HYSPLIT) model with specific humidity analysis, we investigated the water vapor source and influencing factors. The results showed that 1) the isotopic abundance of atmospheric precipitation was depleted in the summer and enriched in winter. dx was lower in summer and higher in winter. The isotopic abundance of precipitation from the plum rain was depleted compared to mean value of the whole-year. 2) There was no significant correlation between δ2H and δ18O of the plum rain (precipitation) with local meteorological factors. However, dx was lower in light rain, reflecting the effect of sub-cloud evaporation. The average dx was higher during plum rain period in years with more total plum rain precipitation. 3) The low-latitude South China Sea and the western Pacific Ocean source area provided water vapor for the plum rain. The shift of moisture source region led to abrupt changes in precipitation isotopes. Our results could provide data support for studies on precipitation isotopes in the monsoon region, as well as a reference point for further understanding the precipitation mechanism of the plum rain and stu-dying the seasonal variability of atmospheric circulation in the East Asian monsoon region.

Determination of contamination sources and geochemical reactions in groundwater of a mine area using Cu, Zn, and S-O isotopes.

To determine contamination sources and pathways, the use of multiple isotopes, including metal isotopes, can increase the reliability of environmental forensic techniques. This study differentiated contamination sources in groundwater of a mine area and elucidated geochemical processes using Cu, Zn, S-O, and O-H isotopes. Sulfate reduction and sulfide precipitation were elucidated using concentrations of dissolved sulfides, δ34SSO4, δ18OSO4, and δ66Zn. The overlying contaminated soil was possibly responsible for the contamination of groundwater at <5 mbgl, which was suggested by low δ65Cu values (0.419-1.120‰) reflecting those of soil (0.279-1.115‰). The existence of dissolved Cu as Cu(I) may prevent the increase in δ65Cu during leaching of contaminated soil in the sulfate-reducing environment. In contrast, the groundwater at >5 mbgl seemed to be highly affected by the contamination plume from the adit water, which was suggested by high SO42- concentrations (407-447 mg L-1) and δ65Cu (0.252-2.275‰) and δ66Zn (-0.105‰-0.362‰) values at a multilevel sampler approaching those of the adit seepages. Additionally, the O-H isotopic ratios were distinguished between <5 mbgl and >5 mbgl. Using δ65Cu and δ66Zn to support the determination of groundwater contamination sources may be encouraged, particularly where the isotopic signatures are distinct for each source.

[Research progress on nitrate isotope coupled multi-tracer tracing groundwater nitrate pollution]. / ç¡é ¸ç›åŒä½ç´ è€¦åˆå¤šç¤ºè¸ªå‰‚æº¯æºåœ°ä¸‹æ°´ç¡é ¸ç›æ±¡æŸ“ç ”ç©¶è¿›å±•.

Nitrate pollution in groundwater has become a global concern. One of the most important issues in controlling the nitrate pollution of groundwater is to identify the pollution source quickly and accurately. In this review, we firstly summarized the isotopic background values of potential sources of nitrate pollution in groundwater in 17 provinces (cities, autonomous regions) and 29 study areas in China, which could provide the fundamental database for subsequent research. Secondly, we reviewed the research progress of nitrate isotopes combined with multiple tracers for tracing nitrate in groundwater, and discussed their applicable conditions, advantages, and disadvantages. We found that halides and microorganisms combined with nitrate isotopes could accurately trace the pollution sources of domestic sewage, excrement and agricultural activities. The combination of Δ17O and nitrate isotopes could effectively distinguish the source of atmospheric deposition of nitrate in groundwater. The combination of groundwater age and nitrate isotopes could further determine the time scale of nitrate pollution. In addition, we summarized the application cases and compared the characteristics of mass balance mixing model, IsoSource model, Bayesian isotope mixing model, and EMMTE model for quantitative identification of nitrate pollution in groundwater. For the complexity and concealment of groundwater pollution sources, the coupling of nitrate isotopes with other chemical and biological tracing methods, as well as the application of nitrate isotope quantitative models, are effective tools for reliably identifying groundwater nitrate sources and transformation processes.

Water temperature affects somatic growth, body condition and oxygen and carbon otolith isotopes of stout whiting (Sillago robusta).

Ocean warming will continue to affect the growth, body condition and geographic distributions of marine fishes and understanding these effects is an urgent challenge for fisheries research and management. Determining how temperature is recorded in fish otolith carbonate, provides an additional chronological tool to investigate thermal histories, preferences and patterns of movement throughout an individual's life history. The influence of three water temperature treatments (22°C, 25°C, and 28°C) on hatchery-reared juvenile stout whiting, Sillago robusta, was tested using a controlled outdoor mesocosm system. Fish were measured for change in length and weight, and body condition was determined using bioelectrical impedance analysis. Sagittal otoliths were analysed for stable oxygen (δ18Ootolith) and carbon (δ13Cotolith) isotopes via isotope ratio mass spectrometry. Whiting kept at 22°C were significantly smaller and had diminished body condition compared to fish in 25°C and 28°C, which did not significantly differ from each other. The δ18O otolith values of stout whiting demonstrated a negative temperature-dependent fractionation relationship which was similar in slope but had a different intercept to the relationships reported for inorganic aragonite and other marine fish species. The δ13C otolith values also showed a negative relationship with water temperature, and the calculated proportion of metabolic carbon M in otoliths differed between fish reared in the coolest (22°C) and warmest (28°C) temperature treatments. Overall, the results suggest that stout whiting may have reached an upper growth threshold between 25°C and 28°C, and that growth and body condition may be optimised during warmer seasons and toward the northerly regions of their distribution. Otolith oxygen thermometry shows promise as a natural tracer of thermal life history, and species-specific fractionation equations should be utilised when possible to prevent errors in temperature reconstructions of wild-caught fish.

Comparison of carbon, nitrogen, and oxygen stable isotope ratios and mercury concentrations in muscle tissues of five beaked whale species and sperm whales stranded in Hokkaido, Japan.

We studied δ13C, δ15N and δ18O values, and total mercury (THg) concentrations in muscle samples from deep-sea predators - five beaked whale species and sperm whales - stranded along the coast of Hokkaido, in the north of Japan in 2010 and 2019. The δ13C, δ15N and δ18O values, THg concentrations, and body length (BL) of Stejneger's beaked whales were similar to those of Hubbs' beaked whales, which belong to the same genus. In contrast, δ13C values, THg concentrations, and BL of Sato's beaked whales were markedly different from those of Baird's beaked whales, which belong to the same genus. Stejneger's and Hubbs' beaked whales living around Hokkaido may compete in their ecological niches, whereas Sato's and Baird's beaked whales may segregate their ecological niches. Although Cuvier's beaked whales and sperm whales belong to different genera and their BLs were significantly different, their δ13C and δ15N values were similar, probably because they can dive and stay in deeper waters than other beaked whale species. The δ13C values in combined samples from all whales increased with increasing BL, probably owing to the larger whale species' dietary preference for squid. The δ13C values in combined samples from all whales were positively correlated with THg concentrations, whereas the δ15N values in the combined samples were negatively correlated. The δ18O values in combined samples from most whales tended to be positively correlated with THg concentrations. These correlations may be explained by a higher THg load from deep-sea feeding than from pelagic feeding and by a feeding shift towards lower trophic levels.

Acid mine drainage from coal mines in the eastern Himalayan sub-region: Hydrogeochemical processes, seasonal variations and insights from hydrogen and oxygen stable isotopes.

Uncontrolled coal mining using non-scientific methods has presented a major threat to the quality of environment, particularly the water resources in eastern himalayan sub-region of India. Water bodies in the vicinity of mining areas are contaminated by acid mine drainage (AMD) that is released into streams and rivers. This study attempted to assess the impact of AMD, deciphering hydrogeochemical processes, seasonal fluctuations, and stable isotope features of water bodies flowing through and around coal mining areas. Self-organizing maps (SOMs) used to separate and categorize AMD, AMD-impacted and non-AMD impacted water from the different study locations for two sampling seasons revealed four clusters (C), with C1 and C2 impacted by AMD, C3 and C4 showing negligible to no impact of AMD. AMD impacted water was SO42- - Mg2+- Ca2+ hydrochemical type with sulphide oxidation and evaporation dominating water chemistry, followed by silicate weathering during both the sampling seasons. Water with negligible-to-no AMD-impact was Mg2+- Ca2+- SO42- to Ca2+ - HCO3- to mixed hydrochemical type with rock weathering and dissolution, followed by ion exchange as major factors controlling water chemistry during both the sampling seasons. Most of physicochemical parameters of C1 and C2 exceeded the prescribed limits, whereas in C3 and C4 water samples, parameters were found within the prescribed limits. Stable isotopes of hydrogen (δ2H) and oxygen (δ18O) during post-monsoon (PoM) varied between -41.04 ‰ and -29.98 ‰, and -6.60 ‰ to -3.94 ‰; and during pre-monsoon (PrM) varied between -58.18 ‰ and - 33.76 ‰ and -8.60 ‰ to -5.46 ‰. Deuterium excess (d-excess) ranged between 1.57 ‰ and 12.47 ‰ during PoM and 5.70 ‰ to 15.17 ‰ during PrM season. The stable isotopes analysis revealed that evaporation, mineral dissolution and mixing with rainwater are the key factors in study area.

Quantitative reconstruction of a single super rainstorm using daily resolved δ18O of land snail shells.

A "once-in-a-millennium" super rainstorm battered Zhengzhou, central China, from 07/17/2021 to 07/22/2021 (named "7.20" Zhengzhou rainstorm). It killed 398 people and caused billions of dollars in damage. A pressing question is whether rainstorms of this intensity can be effectively documented by geological archives to understand better their historical variabilities beyond the range of meteorological data. Here, four land snail shells were collected from Zhengzhou, and weekly to daily resolved snail shell δ18O records from June to September of 2021 were obtained by gas-source mass spectrometry and secondary ion mass spectrometry. The daily resolved records show a dramatic negative shift between 06/18/2021 and 09/18/2021, which has been attributed to the "7.20" Zhengzhou rainstorm. Moreover, the measured amplitude of this shift is consistent with the theoretical value estimated from the flux balance model and instrumental data for the "7.20" Zhengzhou rainstorm. Our results suggest that the ultra-high resolution δ18O of land snail shells have the potential to reconstruct local synoptic scale rainstorms quantitatively, and thus fossil snail shells in sedimentary strata can be valuable material for investigating the historical variability of local rainstorms under different climate backgrounds.

Interpreting life-history traits, seasonal cycles, and coastal climate from an intertidal mussel species: Insights from 9000 years of synthesized stable isotope data.

Understanding past coastal variability is valuable for contextualizing modern changes in coastal settings, yet existing Holocene paleoceanographic records for the North American Pacific Coast commonly originate from offshore marine sediments and may not represent the dynamic coastal environment. A potential archive of eastern Pacific Coast environmental variability is the intertidal mussel species Mytilus californianus. Archaeologists have collected copious stable isotopic (δ18O and δ13C) data from M. californianus shells to study human history at California's Channel Islands. When analyzed together, these isotopic data provide windows into 9000 years of Holocene isotopic variability and M. californianus life history. Here we synthesize over 6000 δ18O and δ13C data points from 13 published studies to investigate M. californianus shell isotopic variability across ontogenetic, geographic, seasonal, and millennial scales. Our analyses show that M. californianus may grow and record environmental information more irregularly than expected due to the competing influences of calcification, ontogeny, metabolism, and habitat. Stable isotope profiles with five or more subsamples per shell recorded environmental information ranging from seasonal to millennial scales, depending on the number of shells analyzed and the resolution of isotopic subsampling. Individual shell profiles contained seasonal cycles and an accurate inferred annual temperature range of ~ 5°C, although ontogenetic growth reduction obscured seasonal signals as organisms aged. Collectively, the mussel shell record reflected millennial-scale climate variability and an overall 0.52‰ depletion in δ18Oshell from 8800 BP to the present. The archive also revealed local-scale oceanographic variability in the form of a warmer coastal mainland δ18Oshell signal (-0.32‰) compared to a cooler offshore islands δ18Oshell signal (0.33‰). While M. californianus is a promising coastal archive, we emphasize the need for high-resolution subsampling from multiple individuals to disentangle impacts of calcification, metabolism, ontogeny, and habitat and more accurately infer environmental and biological patterns recorded by an intertidal species.

Multi-isotope reconstruction of Late Pleistocene large-herbivore biogeography and mobility patterns in Central Europe.

Interpretations of Late Pleistocene hominin adaptative capacities by archaeologists have focused heavily on their exploitation of certain prey and documented contemporary behaviours for these species. However, we cannot assume that animal prey-taxa ecology and ethology were the same in the past as in the present, or were constant over archaeological timescales. Sequential isotope analysis of herbivore teeth has emerged as a particularly powerful method of directly reconstructing diet, ecology and mobility patterns on sub-annual scales. Here, we apply 87Sr/86Sr isotope analysis, in combination with δ18O and δ13C isotope analysis, to sequentially sampled tooth enamel of prevalent herbivore species that populated Europe during the Last Glacial Period, including Rangifer tarandus, Equus sp. and Mammuthus primigenius. Our samples come from two open-air archaeological sites in Central Germany, Königsaue and Breitenbach, associated with Middle Palaeolithic and early Upper Palaeolithic cultures, respectively. We identify potential inter- and intra-species differences in range size and movement through time, contextualised through insights into diet and the wider environment. However, homogeneous bioavailable 87Sr/86Sr across large parts of the study region prevented the identification of specific migration routes. Finally, we discuss the possible influence of large-herbivore behaviour on hominin hunting decisions at the two sites.

Limestone water mixing process and hydrogen and oxygen stable isotope fractionation response under mining action.

North China type coalfield are gradually mining deep, and the mixing of groundwater is intensified. Hydrogen and oxygen isotopes are important elements for tracing groundwater movement. The fractionation response mechanism under mining conditions is not clear. In this paper, combined with numerical simulation, MixSIAR isotope mixing model and other methods, according to the δD, δ18O and hydrochemical information of various water bodies, the impact of coal mining on hydrogen and oxygen isotope fractionation is analyzed from multiple perspectives. The results show that summer soil water is the main source of recharge for limestone water, accounting for 30.7%-41.5%, and the Zhan River is the main source of recharge for limestone water. Before groundwater recharge, evaporation leads to the increase of δ18O in surface water by 0.31‰-5.58‰, water loss by 1.81%-28.00%, the increase of δ18O in soil water by 0.47‰-6.33‰, and water loss by 2.74%-35.80%. Compared with the coal mining layer, the degree of hydrogen and oxygen isotope drift and water-rock interaction in the coal mine stopping layer are significantly improved. The results of numerical simulation show that the pumping activity reduces the 18O concentration in the mining layer. The ion ratio is used as a new variable to eliminate the influence of water-rock interaction when calculating the mixing ratio. The results show that the limestone water is in a state of receiving external recharge, and mixing effect increases the δ18O in limestone water by 0.86‰ on average, and the δD increases by 0.72‰ on average. The research results explain the controlled process of hydrogen and oxygen isotope fractionation under mining conditions, which is of great significance to coal mine safety production.

Developing isotopic proxies to reconstruct the metabolic rates and thermal histories of octopus.

Understanding an animal's metabolic rate and thermal history is pivotal for ecological research. Recent studies have proposed the use of stable carbon and oxygen isotopes (δ13C and δ18O) in biogenic carbonates as proxies of metabolic rate and experienced temperature, respectively, to overcome the challenges of directly measuring these data in the field. Our study represents the first experimental investigation to develop δ13C and δ18O proxies in octopus. Octopus berrima hatchlings were raised in captivity, at varying water temperatures, for up to 110 days. O. berrima statoliths were then subsequently analysed for δ13C and δ18O values. The proportion of metabolically derived carbon, or respired carbon (Cresp), increased as the octopus grew (slope = 0.076, R2 = 0.72), suggesting an influence of somatic growth rate and body mass on δ13C values. Additionally, we identified an inverse correlation between δ18O values and environmental temperature (slope = -0.163, R2 = 0.91), which was subsequently used to develop a thermal reconstruction model. Our experiment aids in interpreting stable isotopic values in statoliths and their application as temperature and metabolic proxies in wild-caught octopus. Such proxies will increase our monitoring capabilities of these ecologically and commercially significant cephalopods and contribute to their conservation and effective management.

Metabolic activity of Planktothrix rubescens and its consequences on oxygen dynamics in laboratory experiment: A stable isotope study.

Fluctuations in dissolved oxygen (DO) contents in natural waters can become intense during cyanobacteria blooms. In a reconnaissance study, we investigated DO concentrations and stable isotope dynamics during a laboratory experiment with the cyanobacterium Planktothrix rubescens in order to obtain insights into primary production under specific conditions. This observation was extended to sub-daily timescales with alternating light and dark phases. Dissolved oxygen concentrations and its isotopes (δ18ODO) ranged from 0.02 to 0.06 mmol · L-1 and from +9.6‰ to +23.4‰. The δ18ODO proved to be more sensitive than concentration measurements in response to metabolic variation and registered earlier shifts to dominance by respiration. Oxygen (O2) contents in the headspace and its isotopes (δ18OO2) ranged from 2.62 to 3.20 mmol · L-1 and from +9.8‰ to +21.9‰. Headspace samples showed less fluctuations in concentration and isotope trends because aquatic processes were hardly able to alter signals once the gas had reached the headspace. Headspace δ18OO2 values were corrected for gas-water equilibration and were determined to be higher than the mean δ18OH2O of -8.7‰. This finding suggests that counteracting respiration was important even during the highest photosynthetic activity. Additionally, headspace analyses led to the definition of a fractionation factor for respiration (αR) of this cyanobacterium with a value of 0.980. This value confirms the one commonly used for cyanobacteria. Our findings may become important for the management of water bodies where decreases in DO are caused by cyanobacteria.

Different responses of oxygen and hydrogen isotopes in leaf and tree-ring organic matter to lethal soil drought.

The oxygen and hydrogen isotopic composition (δ18O, δ2H) of plant tissues are key tools for the reconstruction of hydrological and plant physiological processes and may therefore be used to disentangle the reasons for tree mortality. However, how both elements respond to soil drought conditions before death has rarely been investigated. To test this, we performed a greenhouse study and determined predisposing fertilization and lethal soil drought effects on δ18O and δ2H values of organic matter in leaves and tree rings of living and dead saplings of five European tree species. For mechanistic insights, we additionally measured isotopic (i.e. δ18O and δ2H values of leaf and twig water), physiological (i.e. leaf water potential and gas-exchange) and metabolic traits (i.e. leaf and stem non-structural carbohydrate concentration, carbon-to-nitrogen ratios). Across all species, lethal soil drought generally caused a homogenous 2H-enrichment in leaf and tree-ring organic matter, but a low and heterogenous δ18O response in the same tissues. Unlike δ18O values, δ2H values of tree-ring organic matter were correlated with those of leaf and twig water and with plant physiological traits across treatments and species. The 2H-enrichment in plant organic matter also went along with a decrease in stem starch concentrations under soil drought compared with well-watered conditions. In contrast, the predisposing fertilization had generally no significant effect on any tested isotopic, physiological and metabolic traits. We propose that the 2H-enrichment in the dead trees is related to (i) the plant water isotopic composition, (ii) metabolic processes shaping leaf non-structural carbohydrates, (iii) the use of carbon reserves for growth and (iv) species-specific physiological adjustments. The homogenous stress imprint on δ2H but not on δ18O suggests that the former could be used as a proxy to reconstruct soil droughts and underlying processes of tree mortality.

Advances in Oxygen Isotope Analysis of Phosphate by Electrospray Orbitrap Mass Spectrometry for Studying the Microbial Metabolism of Microorganisms.

Understanding the impact of human activities on the metabolic state of soil and aquatic environments is of paramount importance to implement measures for maintaining ecosystem services. Variations of natural abundance 18O/16O ratios in phosphate have been proposed as proxies for the holistic assessment of metabolic activity given the crucial importance of phosphoryl transfer reactions in fundamental biological processes. However, instrumental and procedural limitations inherent to oxygen isotope analysis in phosphate and organophosphorus compounds have so far limited the stable isotope-based evaluation of metabolic processes. Here, we discuss how recent developments in Orbitrap high resolution mass spectrometry enable measurements of 18O/16O ratios in phosphate and outline the critical mass spectrometry parameters for accurate and precise analysis. Subsequently, we evaluate the types of 18O kinetic isotope effects of phosphoryl transfer reactions and illustrate how novel analytical approaches will give rise to an improved understanding of 18O/16O ratio variations from biochemical processes affecting the microbial phosphorus metabolism.