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Coastal sediments are the main deposition center for allochthonous and autochthonous organic carbon (OC). The discharge of terrestrial biomass, anthropogenic activities, oceanic primary productivity, and natural events contribute to this carbon pool. The OC buried in sediments undergoes alteration through physical, biological and chemical processes, becoming progressively refractory and more likely to be preserved on geological time scales. However, little is known about the rate of bulk OC alteration post weathering and bloom. We incubated coastal sediment slurries with isotopically distinct spikes of C4 corn leaves and cultured phytoplankton, individually and in 1:1 mixture. OC isotopic values and concentrations were probed at different time points to track degradation and incorporation in solid and liquid phases. Both amendments were composed of fresh OC with a high proportion of labile biochemicals (e.g. polysaccharides and proteins). Despite the small differences in their lability, corn leaves were incorporated into the sediments at a slower rate compared to phytoplankton. Following combined spiking of the terrestrial and marine amendments, no sign of synergistic effects was observed in system's response. Despite sediment sensitivity to OC input and the rapid alterations in its properties within the initial days of incubation, swiftly transitioning to a state of minimal change is indicative of a relatively stable system that retained the isotopic imprint of the OC spike for a long time (> 32 days). This isotopic remanence is likely due to heterotrophic bacteria that degrade OC to synthesize their biomass (food stock for successive generations) and incorporate its stable isotope characteristics. Hence, our work sheds light on the kinetics of biogeochemical changes, and recovery time of the system for returning to its pre-perturbation state.

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Organofluorine substances are found in a wide range of materials and solvents commonly used in industry and homes, as well as pharmaceuticals and pesticides. In the environment, organofluorine molecules are now recognized as an important class of anthropogenic pollutants. Fingerprinting organofluorine compounds via their carbon isotope ratios (13C/12C) is crucial for correlating molecules with their source. Here we apply a 19F nuclear magnetic resonance spectroscopy (NMR) technique to obtain the first position-specific carbon isotope ratios for a diverse set of organofluorine molecules. In contrast to traditional isotope ratio mass spectrometry, the 19F NMR method provides 13C/12C isotope ratios at each carbon position where a C-F bond is present, and does not require fragmentation or combustion to CO2, overcoming challenges posed by the robust C-F covalent bonds. The method was validated with 2,2,2-trifluoroethanol, and applied to analyze heptafluorobutanoic acid, 5-fluorouracil and fipronil. Results reveal distinct intramolecular carbon isotope distributions, enabling differentiation of chemically identical molecules. Notably, the NMR method accurately analyzes carbon isotopes within target molecules despite impurities. Potential applications include the detection of counterfeit products and drugs, and ultimately pollution tracking in the environment.

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The analysis of photosynthetic traits has become an integral part of plant (eco-)physiology. Many of these characteristics are not directly measured, but calculated from combinations of several, more direct, measurements. The calculations of such derived variables are based on underlying physical models and may use additional constants or assumed values. Commercially available gas-exchange instruments typically report such derived variables, but the available implementations use different definitions and assumptions. Moreover, no software is currently available to allow a fully scripted and reproducible workflow that includes importing data, pre-processing and recalculating derived quantities. The R package gasanalyzer aims to address these issues by providing methods to import data from different instruments, by translating photosynthetic variables to a standardized nomenclature, and by optionally recalculating derived quantities using standardized equations. In addition, the package facilitates performing sensitivity analyses on variables or assumptions used in the calculations to allow researchers to better assess the robustness of the results. The use of the package and how to perform sensitivity analyses are demonstrated using three different examples.

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Temperature can significantly (P < 0.05) affect plant growth by modifying water use strategies, which are determined by intrinsic water use efficiency (WUEi). Red Heart Chinese Fir (Cunninghamia lanceolata) is one of the most important ecological and economic plantation species in China. However, the C. lanceolata water use strategy in response to increased temperatures and uneven temporal distribution of precipitation during the growing season is rarely reported. In a 7-year-old C. lanceolata plantation, differences in WUEi and C and N concentrations in different organs were analysed by anova, and the δ13C stable isotope, C, and N concentrations in stems determined at different tree heights. Stepwise regression and variance inflation factor were used to remove autocorrelated factors, and structural equation modelling was then used to explore relationships between WUEi and climate and biological factors. WUEi differed significantly between leaf and branch at different standardized precipitation evapotranspiration indices (SPEI). WUEi and N concentration decreased with age. The highest WUEi in branches and leaves were 92.7 and 88.4 µmol·mol-1 in 2020 (SPEI = 0.00), respectively. δ13C increased with relative tree height but N concentration and C/N ratio were not affected. Air temperatures has increased in between 2014 and 2020. WUEi and N concentration decreased with increasing branch and leaf age, but C concentration increased. SPEI significantly positively affected WUEi (P < 0.05), and WUEi was significantly negatively related to C concentration, which is consistent with the trade-off between C and water.

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Invasive macrofauna influence the biophysical state and function of soil, helping to drive ecological changes over time. Many soil-dwelling invertebrates affect soil stability by facilitating or hindering the soil aggregation process, changing the availability of plant and soil organic matter (SOM) for aggregate incorporation, and shifting the predominant mechanisms by which carbon is incorporated into soil aggregates. Using mass fractionation and stable carbon isotope techniques, this 17-month experimental study examined silt-clay-loam mesocosms either infested or not infested with soil-dwelling larvae of the invasive Japanese beetle, Popillia japonica Newman (JB). We hypothesized that larval root-herbivory would promote a pathway of large aggregate formation that features the mixing of digested root tissue with mineral soil and subsequent fecal deposition. These newly deposited, large soil aggregates will then grow by agglomeration of particles, thereby occluding a larger pool of fresh organic carbon, or be broken apart, exposing fresh organic inputs to microbial activity and mineralization processes, depending on soil conditions. Findings show a proportional increase of larger soil size fractions (2- 8 mm) in the rhizosphere of infested soil after 1½ life cycles of the beetle, but a decrease in the smaller soil size fractions (0.053-2 mm). In infested bulk surface soil (0-2.5 cm) carbon increased, primarily due to greater carbon content in the largest size fractions. Carbon also increased in all size fractions, although the proportion of total carbon in fractions was greater only in the largest fractions due to their greater relative abundance. There may also be an increase of microbially derived carbon in the largest size fractions, possibly indicating significant priming effects associated with JB larval herbivory. The implications of these findings for relative stabilization of the bulk surface soil carbon pool in JB-infested soil likely depends on the residence time of, and stable microaggregate formation within these large size fractions.

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Dissolved inorganic carbon (DIC) represents a major global carbon pool and the flux from rivers to oceans has been observed to be increasing. The effect of weathering with respect to increasing DIC has been widely studied in recent decades; however, the influence of dissolved organic matter (DOM) on increasing DIC in large rivers remains unclear. This study employed stable carbon isotopes and Fourier transform ion cyclotron mass spectrometry (FT-ICR MS) to investigate the effect of the molecular composition of DOM on the DIC in the Yangtze River. The results showed that organic matter is an important source of DIC in the Yangtze River, accounting for 40.0 ± 12.1 % and 32.0 ± 7.2 % of DIC in wet and dry seasons, respectively, and increased along the river by approximately three times. Nitrogen (N)-containing DOM, an important composition in DOM with a percentage of ∼40 %, showed superior oxidation state than non N-containing DOM, suggesting that the presence of N could improve the degradable potential of DOM. Positive relationship between organic sourced DIC (DICOC) and N-containing DOM formulae indicated that N-containing DOM is crucial to facilitate the mineralization of DOM to DICOC. N-containg molecular formular with low H/C and O/C ratio were positively correlated with DICOC further verified these energy-rich and biolabile compounds are preferentially decomposed by bacteria to produce DIC. N-containing components significantly accelerated the degradation of DOM to DICOC, which is important for understanding the CO2 emission and carbon cycling in large rivers.

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The present article introduces Zanadamu, a comprehensive geo-temporal-referenced dataset that amalgamates all published stable isotope carbon and oxygen measurements on tooth enamel from African hominins, dated between 4.4 and 0.005 Ma. Zanadamu serves as a research tool for investigating hominin evolution by facilitating the examination of how different hominin species explored food resources and interacted with their local paleoenvironments. The dataset is structured in a machine-readable format, and its metadata organization allows for facile statistical analyses and comparisons with other types of isotopic records, including ancient and modern humans and other primates. Zanadamu is part of the AfriArch data initiative, which aims at compiling datasets for the study of ancient Africa. This an active initiative, and we strive to update Zanadamu as novel data becomes available.

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Dissolved organic matter (DOM) transported by inflowing rivers can considerably contribute to the organic loadings of lakes. The current study characterized the DOM properties and source apportionment in the inflowing rivers of Dianchi Lake, the sixth largest freshwater lake in China suffering from organic pollution, during the rainy season by using spectroscopic and carbon stable isotope techniques, and the regulation role of land use was assessed. The results showed that land use (urbanized, agricultural, or mixed) largely affected DOM properties. Greater concentrations and fluorescence intensities of DOM with low aromaticity and dominant autochthonous sources were observed in the urban rivers than in the agricultural rivers. The proportion of humic-like substances increased, while that of tryptophan-like matter decreased from upstream to downstream of two main urban rivers. DOM in the agricultural rivers was characterized by more amounts of aromatic humic-like substances with dominant allochthonous sources compared to that in the urban rivers. Stable isotope analysis showed that the decomposition of macrophytes and input of terrestrial sources from C3 plant-dominated soil and sewage were the major DOM origins in the rivers. The positive linear relationship between the chemical oxygen demand (COD) concentration and fluorescence intensities of terrigenous DOM components implied the necessity of controlling exogenous inputs to alleviate organic pollution in the Dianchi Lake.

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Trees continuously regulate leaf physiology to acquire CO2 while simultaneously avoiding excessive water loss. The balance between these two processes, or water use efficiency (WUE), is fundamentally important to understanding changes in carbon uptake and transpiration from the leaf to the globe under environmental change. While increasing atmospheric CO2 (iCO2 ) is known to increase tree intrinsic water use efficiency (iWUE), less clear are the additional impacts of climate and acidic air pollution and how they vary by tree species. Here, we couple annually resolved long-term records of tree-ring carbon isotope signatures with leaf physiological measurements of Quercus rubra (Quru) and Liriodendron tulipifera (Litu) at four study locations spanning nearly 100 km in the eastern United States to reconstruct historical iWUE, net photosynthesis (Anet ), and stomatal conductance to water (gs ) since 1940. We first show 16%-25% increases in tree iWUE since the mid-20th century, primarily driven by iCO2 , but also document the individual and interactive effects of nitrogen (NOx ) and sulfur (SO2 ) air pollution overwhelming climate. We find evidence for Quru leaf gas exchange being less tightly regulated than Litu through an analysis of isotope-derived leaf internal CO2 (Ci ), particularly in wetter, recent years. Modeled estimates of seasonally integrated Anet and gs revealed a 43%-50% stimulation of Anet was responsible for increasing iWUE in both tree species throughout 79%-86% of the chronologies with reductions in gs attributable to the remaining 14%-21%, building upon a growing body of literature documenting stimulated Anet overwhelming reductions in gs as a primary mechanism of increasing iWUE of trees. Finally, our results underscore the importance of considering air pollution, which remains a major environmental issue in many areas of the world, alongside climate in the interpretation of leaf physiology derived from tree rings.

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Stable carbon isotope analysis has proven utility for reconstructing dietary information in humans in past populations. The usefulness of stable carbon for forensic geolocation has been little investigated, largely because of the globalization of the human diet seemingly rendering it inconsequential. This study queried this assumption at a country-wide level on a known sample group. Stable carbon isotope values were obtained from human enamel with known biographical and geographical information to determine whether stable carbon, when paired with stable oxygen isotope values, could differentiate Canadians from non-Canadians. Samples originating outside of Canada were separated into three regions, and a linear discriminant analysis was used to generate discriminant functions that best separate the regions according to the stable carbon and oxygen isotope values. The results revealed two functions, where the first function explained 92.1% and the second 7.9% of the variance. Although some overlap in stable carbon and oxygen values was observed for individuals from both the United States and Canada, differences were observed between those from Canada and other geographical regions. This study demonstrated that pairing the dietary isotope carbon with the geolocator stable oxygen isotope, produced an interesting separation geographically, one that might well be helpful when attempting a geolocation query on unknown human remains.

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Recent climate extremes in Mongolia have ignited a renewed interest in understanding past climate variability over centennial and longer time scales across north-central Asia. Tree-ring width records have been extensively studied in Mongolia as proxies for climate reconstruction, however, the climate and environmental signals of tree-ring stable isotopes from this region need to be further explored. Here, we evaluated a 182-year record of tree-ring δ13C and δ18O from Siberian Pine (Pinus sibirica Du Tour) from a xeric site in central Mongolia (Khorgo Lava) to elucidate the environmental factors modulating these parameters. First, we analyzed the climate sensitivity of tree-ring δ13C and δ18O at Khorgo Lava for comparison with ring-width records, which have been instrumental in reconstructing hydroclimate in central Mongolia over two millennia. We also compared stable isotope records of trees with partial cambial dieback ('strip-bark morphology'), a feature of long-lived conifers growing on resource-limited sites, and trees with a full cambium ('whole-bark morphology'), to assess the inferred leaf-level physiological behavior of these trees. We found that interannual variability in tree-ring δ13C and δ18O reflected summer hydroclimatic variability, and captured recent, extreme drought conditions, thereby complementing ring-width records. The tree-ring δ18O records also had a spring temperature signal and thus expanded the window of climate information recorded by these trees. Over longer time scales, strip-bark trees had an increasing trend in ring-widths, δ13C (and intrinsic water-use efficiency, iWUE) and δ18O, relative to whole-bark trees. Our results suggest that increases in iWUE at this site might be related to a combination of leaf-level physiological responses to increasing atmospheric CO2, recent drought, and stem morphological changes. Our study underscores the potential of stable isotopes for broadening our understanding of past climate in north-central Asia. However, further studies are needed to understand how stem morphological changes might impact stable isotopic trends.

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Black carbon (BC), the highly recalcitrant aromatic carbonaceous from the incomplete combustion of fossil fuel and biomass, is an important carbon sink in carbon cycle. Char and soot, the main components of BC, have significantly different origin and physicochemical characteristics (particle sizes and resultant transportability). The limited understanding of char and soot sources leads to poor insight into the effect of BC on carbon cycle. Sources of char and soot were investigated in this study using stable carbon isotopes to study the effect of BC on the organic carbon pool in a lake, thereby improving the knowledge of lacustrine carbon cycling. The concentration of BC in Taihu Lake ranged from 0.0 to 0.7 mg·L-1and accounted for 10.9 ± 4.7% of the particulate organic carbon. The spatial-mean δ13C values of BC, char, and soot were -23.2 ± 2.0‰, -23.5 ± 2.2‰, and -22.9 ± 1.6‰, respectively. The BC in water was primarily derived from fossil fuels (66.0 ± 9.3%), with liquid fossil fuel accounting for 48.2 ± 13.2% of the BC. The contribution of liquid fossil fuel to soot (49.3%) was much higher than that to char (36.1%); correspondingly, the contributions of biomass and coal to soot (29.2% and 21.5%) were lower than those to char (38.1% and 25.8%). The contribution of liquid fossil fuel combustion to organic carbon (OC), char, and soot gradually increased from 31.9% to 49.3%. Biomass and coal combustion primarily contributed to char (38.1% and 25.8%) and OC (37.5% and 30.6%). The source apportionment of BC, char, and soot revealed the influence of anthropogenically driven BC, char, and soot on the lake and, by extension, to the global carbon cycle.

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The impact of climate extremes on forest ecosystems is poorly understood but important for predicting carbon and water cycle feedbacks to climate. Some knowledge gaps still remain regarding how drought-related adjustments in intra-annual tree-ring characteristics directly impact tree carbon and water use. In this study we quantified the impact of an extreme summer drought on the water-use efficiency and carbon sequestration of four mature Norway spruce trees. We used detailed observations of wood formation (xylogenesis) and intra-annual tree-ring properties (quantitative wood anatomy and stable carbon isotopes) combined with physiological water-stress monitoring. During 41 d of tree water deficit, we observed an enrichment in 13 C but a reduction in cell enlargement and wall-thickening processes, which impacted the anatomical characteristics. These adjustments diminished carbon sequestration by 67% despite an 11% increase in water-use efficiency during drought. However, with the resumption of a positive hydric state in the stem, we observed a fast recovery of cell formation rates based on the accumulated assimilates produced during drought. Our findings enhance our understanding of carbon and water fluxes between the atmosphere and forest ecosystems, providing observational evidence on the tree intra-annual carbon sequestration and water-use efficiency dynamics to improve future generations of vegetation models.

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Andean wetlands hold extremophilic communities adapted to live in harsh conditions. Here, we investigated the microbial ecology of three high-altitude hypersaline ponds from La Puna region (Argentina) showing an increasing extent of desiccation by analyzing their lipid sedimentary record. We recreated the microbial community structure and the carbon metabolisms in each lacustrine system based on the molecular distribution of lipid biomarkers and their compound-specific carbon and hydrogen isotopic signatures. We detected lipid compounds considered to be biomarkers of cyanobacteria, sulfate-reducing bacteria, purple sulfur bacteria, and archaea in the three Andean ponds, as well as diatoms in the intermediate salinity system. The relative abundance of purple sulfur and sulfate-reducing bacteria decreased with salinity, whereas cyanobacteria and archaea decreased their relative abundance in the mid-saline pond to increase it again and became both prevailing at the highest salinity. Carbon fixation in the three ponds was driven by a combination of the reductive tricarboxylic acid cycle, the reductive pentose phosphate cycle, and the reductive acetyl-CoA pathway. This work is the first to describe molecular and isotopic lipid fingerprints in wetlands from the central Andean Puna, and serves as a basis for further biogeochemical studies in the area.

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BACKGROUND: With strong environmental and geographic filtration, vertebrates incapable of flying and swimming are often extirpated from island ecosystems. Minami-Daito Island is an oceanic island in Okinawa, Japan that harbors the Daito flying fox (Pteropus dasymallus daitoensis), a subspecies of the fruit bat and the only extant mammal endemic to the island. However, the skeleton of a cave-dwelling bat Rhinolophus sp. and fossil guano were briefly reported in a previous study. METHODS: Here, we present evidence for the anthropogenic extirpation of two species of cave-dwelling bats (Miniopterus sp. & Rhinolophus sp.) from Minami-Daito Island. Our goal is to reliably constrain the ages of the extirpated bat species by a multiproxy approach. Because skeletal materials did not preserve sufficient bone collagen for direct radiocarbon dating, we alternatively examined guano-like deposits based on SEM observation and Fourier-transform infrared spectroscopy (FTIR) along with stable carbon and nitrogen isotope analyses for possible indirect dating. We also examined stable carbon isotopes in bone apatite, assuming that an isotopic signal of C4 plants on the bat bones links to sugarcane plantation on the island based on the historical knowledge that early human settlers quickly replaced the island's native C3 forests with sugarcane (C4 perennial grass) plantation from 1900 onward. RESULTS: Our cave survey documents the remains of Miniopterus sp. from the island for the first time. Based on the unique taphonomic conditions (unpermineralized bones, disarticulated skeletons closely scattered without sediment cover, various degrees of calcite crystal growth around bones) and a radiocarbon age of a humic sample, we suggest that the maximum age constraint of Miniopterus sp. and Rhinolophus sp. is 4,640 calBP. Based on a series of analyses, we conclude that the guano-like deposits are composed not of bat guano but mainly of humic substances; however, a hydroxyapatite crust associated with bat-lying stalagmites may be derived from bat feces. Stable carbon isotope analysis of bone apatite revealed C4 signals in various degrees, confirming that small populations of cave-dwelling bats persisted on Minami-Daito Island after 1900. CONCLUSIONS: The results of this study indicate that these populations remained rather small and did not leave many generations and that the estimated ages can be bracketed from 4,640 calBP to the post-1900 (perhaps, until the 1950s). They likely faced a continuously high mortality risk due to severe anthropogenic stresses on the island, where most of the forests were turned into sugarcane plantations within a few decades in the early 20th century. A result of hearing surveys to local residents suggests the latest remnants most likely disappeared on the island concurrently with the introduction of chemical pesticides after World War II.

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Recalcitrant dissolved organic carbon (RDOC) resulting from microbial carbon (MCPs) holds promise as a relatively long-term natural carbon sink in marine environments. However, the RDOC formation mechanism remains uncertain in terrestrial aquatic systems. To determine the microbial impacts on autochthonous dissolved organic carbon (DOC), RDOC formation, and the critical influencing bacteria species, spatial changes in hydrochemistry, carbon isotopes, and microbial diversity were investigated in water samples from the karstic Lijiang River, southwest China. Samples were collected at various locations along the river system in May and July 2017. The biodegradable DOC (BDOC), RDOC, soil sourced DOC (SDOC), submerged aquatic vascular plant sourced DOC (PDOC) and microbial sourced DOC (MDOC) were calculated using the in-situ microbial incubation method, stable carbon isotopes and C/N ratio. RDOC accounted for 67% to 93% of DOC concentrations, measuring 1.3 mg/L and 1.2 mg/L in May and July, respectively. In May, BDOC concentrations increased by 0.05 mg/L from 0.18 mg/L to 0.23 mg/L, but decreased by 0.43 mg/L from 0.66 mg/L to 0.23 mg/L in July. The spatiotemporal variation of BDOC indicated photosynthesis was the main BDOC source and induced high autochthonous DOC formation, especially in May. However, RDOC was the dominant accumulation component in Lijiang River. MDOC increased by 0.86 mg/L from 0 to 0.86 mg/L in May and 0.78 mg/L from 0.10 mg/L to 0.88 mg/L in July, which was the dominant accumulated DOC and RDOC component. The abundance of Sporichthyaceae accounted for 3.4%-22.6% in May and Novosphingobium accounted for 3.5%-34.0% in July. These were the critical bacteria species induced MDOC formation, which were confirmed by their abundances in KEGG pathway modules determined by PICRUAST2. These results demonstrate that heterotrophic bacteria dominate autochthonous DOC and RDOC formation in the karst surface river, which is valuable for understanding organic carbon cycling in karstic aquatic systems.

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Methane (CH4) formation by vegetation has been studied intensively over the last 15 years. However, reported CH4 emissions vary by several orders of magnitude, thus making global estimates difficult. Moreover, the mechanism(s) for CH4 formation by plants is (are) largely unknown.Here, we introduce a new approach for making CH4 formation by plants clearly visible. By application of 13C-labeled dimethyl sulfoxide (DMSO) onto the leaves of tobacco plants (Nicotiana tabacum) and Chinese silver grass (Miscanthus sinensis) the effect of light and dark conditions on CH4 formation of this pathway was examined by monitoring stable carbon isotope ratios of headspace CH4 (δ13C-CH4 values).Both plant species showed increasing headspace δ13C-CH4 values while exposed to light. Higher light intensities increased CH4 formation rates in N. tabacum but decreased rates for M. sinensis. In the dark no formation of CH4 could be detected for N. tabacum, while M. sinensis still produced ~50% of CH4 compared to that during light exposure.Our findings suggest that CH4 formation is clearly dependent on light conditions and plant species and thus indicate that DMSO is a potential precursor of vegetative CH4. The novel isotope approach has great potential to investigate, at high temporal resolution, physiological, and environmental factors that control pathway-specific CH4 emissions from plants.

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The change in hydrodynamics by damming facilitates the terrestrial biological­carbon-pump (BCP) effect and promotes the generation and burial of autochthonous organic carbon (OCauto). To constrain the burial fluxes of OCauto is crucial when assessing the role of inland waters in the global carbon cycle as OCauto originating mainly from weathering-derived dissolved inorganic carbon is overlooked in current global carbon budgeting. Here we examined the elemental and carbon isotopic compositions of the settling organic matter collected by sediment traps in three subtropical karst reservoirs (Hongfenghu, Pingzhai and Puding), SW China. The results show that 30- 60% of the settling OC in the studied reservoirs is autochthonous. The proportion of OCauto correlates inversely with OC's settling flux. Interestingly, Hongfenghu Reservoir, featured by the highest trophic state and POC concentration, has the highest fraction of OCauto but the lowest settling flux of OCauto among three reservoirs. The ballast effect of biogenic silica and lithogenic materials, rather than the aquatic primary productivity, is supposed to be the primary factor that governs the settling flux of OCauto in the studied reservoirs. Finally, it is estimated that the settling flux of OCauto in the three reservoirs is 47- 119 g C/m2/yr while the burial flux of OCauto is 10- 26 g C/m2/yr if assuming about 80% of OCauto is remineralized after sedimentation. This study demonstrates for the first time the role of biogenic silica and lithogenic materials' input in reservoir OC's settling which may be the further important due to the strengthening agricultural activity and the increasing fast-flow hydroelectric reservoirs.

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Tam Pà Ling, a cave site in northeastern Laos, has yielded the earliest skeletal evidence of Homo sapiens in mainland Southeast Asia. The reliance of Pleistocene humans in rainforest settings on plant or animal resources is still largely unstudied, mainly due to poor collagen preservation in fossils from tropical environments precluding stable nitrogen isotope analysis, the classical trophic level proxy. However, isotopic ratios of zinc (Zn) in bioapatite constitute a promising proxy to infer trophic and dietary information from fossil vertebrates, even under adverse tropical taphonomic conditions. Here, we analyzed the zinc isotope composition (66Zn/64Zn expressed as δ66Zn value) in the enamel of two teeth of the Late Pleistocene (63-46 ka) H. sapiens individual (TPL1) from Tam Pà Ling, as well as 76 mammal teeth from the same site and the nearby Nam Lot cave. The human individual exhibits relatively low enamel δ66Zn values (+0.24‰) consistent with an omnivorous diet, suggesting a dietary reliance on both plant and animal matter. These findings offer direct evidence of the broad utilization of resources from tropical rainforests by one of the earliest known anatomically modern humans in Southeast Asia.

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Methane observed in soil atmosphere above active and abandoned bituminous coal mines has a thermogenic (coalbed) and/or microbial (produced by anaerobic bacteria or resulted from in situ coal biodegradation) origin or it may be a mixture of gases generated from various sources. Identification of the origin of methane may support or refute the thesis on the uncontrolled migration of mine gases in rock formations followed by their emission to the atmosphere at coal extraction sites. Surface geochemical surveys were carried out in the vicinity of the decommissioned mine shafts at the Murcki-Staszic Coal Mine, located in the Upper Silesian Coal Basin (southern Poland). Over a 3-month period, measurements were carried out cyclically at 2 locations. Totally, 43 fixed geochemical probes were installed in the area of the Murcki II "Stanislaw" Shaft, in which measurements were carried out in six sessions. Next 29 probes were installed in the area of the Staszic III Shaft, where measurements were taken twice. Each measurement included concentrations of 5 components (methane, non-methane volatile organic compounds, total hydrocarbons, carbon dioxide and oxygen), which provided a total number of 1405 individual analytical determinations. For measurements, portable EcoProbe 5 instrument was used. The stable carbon isotope composition of methane and carbon dioxide was analyzed in selected 10 samples. The isotopic composition of hydrogen in methane was also measured in one sample. The comparative material consisted of eight samples of soil gases and two samples of mine gases, which were used as reference 'soil' gases. The isotopic analyses were conducted using a mass spectrometry method. Based on the results of our analyses, it is stated that both the Murcki II "Stanislaw" and the Staszic III shafts were properly decommissioned. The successful sealing of mine shafts prevented mine gases from migration through the shaft into the atmosphere. However, at a single geochemical probe located more than 100 m from the former shaft center, methane concentration in soil gases reached over 1 vol%. This confirms the general observation that mine gas migrates from coal seams and/or gobs through crushed rocks into the atmosphere. The stable carbon isotope analysis of methane and carbon dioxide as well as stable hydrogen isotope analysis of methane suggest that methane in the soil atmosphere is of thermogenic origin with minor contribution of microbial component.