Isotopic Space Research Articles

Comprehensive Insight into Regular Damped Oscillatory Structures from Effective Electromagnetic Form Factor Data of Some Mesons and Nucleons

Regular damped oscillatory structures from the “effective” electromagnetic form factors of the hadrons h=π±,K±,K0,p,n were investigated. The “effective” electromagnetic form factor behaviors were calculated from the experimental data on the total cross-sections σtot(e+e−→hh¯) with errors. The apparent oscillations were observed for the first time for the proton, and we show, also taking other hadrons into consideration, that they are an arbitrary artifact resulting from a very simplistic theoretical description based on an elementary three-parameter model. If the data are described by a more appropriate and physically well-founded Unitary and Analytic model, then the oscillations disappear. In spite of this, if the three-parameter model is used to describe the “effective” electromagnetic form factor data, an interesting phenomenon is observed. The oscillations are opposite for particles which form an isospin doublet. By using the physically well-founded Unitary and Analytic model, it is demonstrated that this feature originates from the special transformation properties of the electromagnetic current of the corresponding particles in the isotopic space.

Divergent ornamentation within a single population of the barn swallow.

Differential migration strategies favour different sets of characteristics, including sexually selected ornamentation. Such phenotypic variation is particularly evident in a population with partial migration, where migrants and non-migrants co-exist. Partial migration provides insights into the link between migration, local environment and ornamentation, although empirical studies remain scarce. Here, we studied the plumage traits of barn swallows (Hirundo rustica) in southern Japan, where both winterings and migrants breed sympatrically. We further examined this relationship with multiple isotopes (δ2H, δ13C, δ15N and δ34S), which provides insight into their moulting habitat. Among males, winterings and migrants differed in their morphological traits: wintering males had shorter wings, which suggests the high demand for flight apparatus in migratory birds. Moreover, wintering males had larger white tail spots and less colourful throat patches than migratory males, indicating ornament divergence between them. Wintering males had a significantly smaller isotopic space when examining the combinations of δ34S with the other isotopes compared to migratory males, which indicates a differential geographic range between them, perhaps because of the limited variation in the distance to the sea in wintering males. As in males, wintering females had a significantly smaller isotopic space than migrant females, but there were few morphological differences between migratory and wintering females. Instead, some morphological traits were related to isotope values in females. These results indicate sex-specific linkage between migration, local environment, and ornamentation.

Isotopic niches reveal the impact of topmouth gudgeon and gibel carp on native crucian carp

Invasive species pose a major threat to natural ecosystems and directly outcompete many native species, placing them at imminent threat of extinction. The topmouth gudgeon (Pseudorasbora parva) is on the EU’s blacklist of invasive freshwater species and threatens biodiversity, especially in wetland and floodplain ecosystems, aquacultures and village ponds. The crucian carp (Carassius carassius) is native to Europe and its populations have declined in large part of its native range, with invasive gibel carp (C. gibelio) suspected as a major cause of its decline. Invasions by topmouth gudgeon have been implicated in the decline of crucian carp populations but this still needs to be verified. The aim of this study was to evaluate by the experimental approach the competitive interaction between the two species, topmouth gudgeon and crucian carp, focusing on isotopic niche sizes and their overlap in syntopy. A four-month mesocosm experiment was performed to determine the isotopic niche of crucian carp and topmouth gudgeon living alone and in syntopy. Additionally, stable isotope data were collected at the sites where the two species co-occur to compare niche sizes and overlaps. Experimental data showed that the isotopic space of topmouth gudgeon responded more flexibly (reducing niche size at syntopy) than that of the crucian carp and confirmed a high isotopic niche overlap between the species. Field studies have shown that topmouth gudgeon has invaded the isotopic niche of the crucian carp, especially when another invasive species, the gibel carp, lived in the community (25% at 40% ellipse area and 50% at 95% ellipse area). When only the topmouth gudgeon and crucian carp were present in the field, the overlap was lower (3% and 48%, respectively) and directional overlap modelling showed that the crucian carp was more likely to invade the isotopic niche of topmouth gudgeon than vice versa. The data indicated that competition between crucian carp and topmouth gudgeon is likely, especially in syntopy with other invasive species. This study shows that the feeding plasticity of topmouth gudgeon likely facilitates its establishment outside its native range and, due to high isotopic niche overlap, threatens native fish with similar feeding ecology with competitive displacement.

Discovery and identification of natural alkaloids with potential to impact insulin resistance syndrome in Cyclocarya paliurus. (Batal) leaves by UPLC-QTOF-MS combined with HepG2 cells

Cyclocarya paliurus (Batal.) leaves, which contain a range of bioactive compounds, have been used as a traditional Chinese medicine homologous food since ancient times. However, there is a paucity of literature on comprehensive studies of alkaloids in the leaves of Cyclocarya paliurus (Batal.). For the first time, this study aimed to discover and identify alkaloids extracted from Cyclocarya paliurus (Batal.) leaves by ultra-high performance liquid chromatography-quadrupole-time-of-flight tandem mass spectrometry (UPLC-QTOF-MS). A total of ten alkaloids have been identified from Cyclocarya paliurus (Batal.) leaves based on accurate mass spectra (mass accuracy, isotopic spacing and distribution) and comparison to fragmentation spectra reported in the literature. In vitro, alkaloids alleviated insulin resistance by increasing glucose consumption and glycogen content in insulin resistance HepG2 cells. The RNA-seq and western blotting results showed that alkaloids could upregulate the expression of phosphatidylinositol 3-kinase (PI3K), and increase the phosphorylation of insulin receptor protein kinase B (AKT). This study not only clarified the chemical constituents and revealed that diverse alkaloids also presented from Cyclocarya paliurus (Batal.) leaves, also, it will provide chemical information on potential compounds for developing new drugs.

Authigenic quartz reveals the triple oxygen isotope composition and diagenetic temperature of saline brines

Triple oxygen isotope compositions of authigenic minerals are an emerging tool for the reconstruction of fluid temperatures and the fluid isotopic composition. In this study, we analyzed euhedral authigenic quartz crystals from a halite deposit of the Upper Permian Zechstein evaporitic basin for their triple oxygen isotope composition using laser fluorination isotope ratio mass spectrometry. In the triple oxygen isotope space, additional information, such as the triple oxygen isotope composition of the ambient water, provides insights into equilibrium conditions during quartz formation that cannot be identified from δ18O alone. The triple oxygen isotope composition of authigenic quartz shows, that single oxygen isotope (δ18O) thermometry is not applicable for samples from evaporitic environments, where the fluids' δ18O deviates from dynamic oxygen isotope equilibrium. By combining the Craig and Gordon evaporation model with H2O – SiO2 triple oxygen isotope equilibrium fractionation, we reconstruct the formation temperature of authigenic quartz and the triple oxygen isotope composition of the marine-derived saline brine pore fluid in equilibrium with the quartz. We obtain temperatures of 90 to 130 °C that is interpreted as crystallization temperatures of microcrystalline quartz in pore fluid of halite during burial diagenesis. The triple oxygen isotope composition of authigenic quartz from evaporitic environments is suited as a geochemical tracer for fluid oxygen isotope compositions and ancient fluid or diagenetic temperatures.

Niche partitioning and individual specialisation in resources and space use of sympatric fur seals at their range margin

Ecological theory predicts niche partitioning between high-level predators living in sympatry as a mechanism to minimise the selective pressure of competition. Accordingly, male Australian fur seals Arctocephalus pusillus doriferus and New Zealand fur seals A. forsteri that live in sympatry should exhibit partitioning in their broad niches (in habitat and trophic dimensions) in order to coexist. However, at the northern end of their distributions in Australia, both are recolonising their historic range after a long absence due to over-exploitation, and their small population sizes suggest competition should be weak and may allow overlap in niche space. We found some niche overlap, yet clear partitioning in diet trophic level (δ15N values from vibrissae), spatial niche space (horizontal and vertical telemetry data) and circadian activity patterns (timing of dives) between males of each species, suggesting competition may remain an active driver of niche partitioning amongst individuals even in small, peripheral populations. Consistent with individual specialisation theory, broad niches of populations were associated with high levels of individual specialisation for both species, despite putative low competition. Specialists in isotopic space were not necessarily specialists in spatial niche space, further emphasising their diverse individual strategies for niche partitioning. Males of each species displayed distinct foraging modes, with Australian fur seals primarily benthic and New Zealand fur seals primarily epipelagic, though unexpectedly high individual specialisation for New Zealand fur seals might suggest marginal populations provide exceptions to the pattern generally observed amongst other fur seals.

Adfluvial smallmouth bass in a tributary of Lake Huron

Fish exploit opportunities within aquatic ecosystems to increase their likelihood of survival, growth, and reproduction, ultimately to maximize fitness over the entire life cycle. Fitness is increased by moving to find abiotic and biotic conditions suitable for various life history stages. Smallmouth bass (Micropterus dolomieu) are known to spawn in lakes and flowing waters displaying high nest site fidelity in both environments. Some populations of smallmouth bass are adfluvial, living as adults in lakes and ascending rivers to spawn. However, this life history variant is poorly understood, particularly in the Great Lakes. The objective of our study was to determine if smallmouth bass migrate 13 km upstream to a barrier in the Maitland River from Lake Huron. Stable isotopes were used to make inferences about the migratory status of Maitland River smallmouth bass. We found significant separation in the isotopic space for adult bass captured downstream of a migration barrier (mean δ13C = −18.93 ‰; mean δ15N = 11.02 ‰) compared to bass found upstream (mean δ13C = −26.58 ‰; mean δ15N = 15.29 ‰) river segments. Stable isotope values for juvenile bass, forage fishes, and invertebrates all grouped in similar δ13C isotopic space across the lower and upper river segments. Adfluvial smallmouth bass are underappreciated, yet an important life history variant supporting population biodiversity in the Great Lakes.

Triple oxygen isotope systematics of CO2 hydroxylation

Kinetic isotope effects occurring during carbonate precipitation impact the accuracy of paleoclimate records. One rate-limiting process is CO2 absorption, which, at high pH, primarily proceeds through hydroxylation, where aqueous CO2 and OH− react to form HCO3−. In this study, we investigated the triple oxygen isotope fractionation (18O/16O and 17O/16O) associated with the hydroxylation reaction. We experimentally determined the extent of the kinetic isotope effects superimposed on the reacting CO2 and OH− during hydroxylation, using high-pH precipitation reactions. These results were compared to the equilibrium triple oxygen isotope fractionation between H2O and OH− modeled using quantum chemical computations.Our quantum chemical modeling confirms the previously suggested equilibrium θeq.H2O/OH- of 0.5296 at 25 °C. Our empirical data show a kinetic isotope effect superimposed on the OH− involved in the hydroxylation reaction of approximately −16.4‰ for the fractionation of 18O/16O and a corresponding slope of 0.514 in triple oxygen isotope space. The θeffectiveH2O/OH- for the fractionation between water and the reacting OH− is 0.523.In order to identify and potentially correct kinetic isotope effects in carbonates, it is important to understand the fractionations occurring during precipitation. Our results enable a more accurate modeling of kinetic isotope effects in triple oxygen isotope space, particularly the slope of hydroxylation. The θhydroxylation is dependent on the isotope composition of the ambient water, CO2, and the temperature. We estimate that θhydroxylation is approximately 0.532 for carbonates growing in 25 °C seawater.

Functional structure and diversity of marine benthos reflect food availability and quality, as evidenced by isotopic diversity

AbstractOrganic matter (OM) resources shape not only the trophic diversity of benthic communities but also the diversity of benthic functional traits. The resulting community structure has a direct effect on many ecosystem processes and functions. Still, the relationship between functional diversity of marine benthos and its trophic diversity in response to the variability of food remains poorly investigated. To explore this relationship we focused on the assessment of various facets of macrobenthic diversity in two temperate coastal areas (southern Baltic Sea) characterized by similar species pool and habitat properties but different OM sources and supplies. We also identified spatio‐temporal patterns of functional structure and assessed, which OM properties had the strongest influence on benthic communities. In our study, functional space dispersion followed isotopic space dispersion, reflecting the positive relationship between food variability and ecological functions of benthic communities. Moreover, functional structure in shallow areas was more location‐specific in comparison to deeper areas, and this was significantly related to OM parameters. Higher OM variability close to the river mouth prevented the community from becoming dominated by one specialized species, whereas limited OM supply at shallow open coast lowered the diversity by enabling stronger competitor to dominate the community. In more offshore areas, local OM variability ceased and hence, communities tended to reflect similar trophic and functional patterns. Our study demonstrates that functional and isotopic diversity approaches can be effectively combined to better understand mechanisms driving benthic community structure and confirm that greater variability in OM supply increases diversity of benthic communities.

C and N stable isotopes enlighten the trophic behaviour of the dugong (Dugong dugon)

The dugong (Dugong dugon), a large marine mammal herbivore of the Indo-Pacific, is vulnerable to extinction at a global scale due to a combination of human-related threats including habitat degradation. The species forages on seagrass habitats (marine phanerogams) and plays a key role in the functioning and sensitivity of these declining coastal ecosystems. The trophic behaviour and plasticity of dugong populations in response to extrinsic and intrinsic factors are therefore crucial features to both dugong and seagrass conservation. Yet, this knowledge remains limited to few visual observations and analyses of mouth, stomach or faecal contents of stranded individuals. We take advantage of a long-term monitoring of stranded individuals from the endangered New Caledonian population to depict features of dugongs’ trophic ecology from Carbon and Nitrogen stable isotopes. A total of 59 dugong skin samples were used to portrait the stable isotope niche of dugongs according to their sex and maturity. In light of previous work conducted in New Caledonia, a subset of these samples was used to model the trophic mix of dugong males and females. Our stable isotope mixing models used C and N isotope values of 10 taxa bbelonging to five divisions of metazoans, plants, and chromists. Our results represent the first estimate of the species dietary niche in the isotopic space. They suggest that the diet of dugong calves overlaps more with that of adult females (δ13C: − 6.38 ± 1.13 ‰; δ15N: 2.49 ± 1.10 ‰) than males (δ13C: − 5.92 ± 1.10 ‰; δ15N: 3.69 ± 1.28 ‰). Further, we highlight differences in the expected trophic mix of dugong adult males and females. From these, we formulate a sex-specific foraging behaviour hypothesis in dugongs, whereby lactating females could forage over smaller spatial ranges but more diverse food sources thanmales. The study emphasizes the importance of long-term stranding monitoring programs to study the ecology of marine mammals.. Finally, it depicts an ecological feature that may contribute to the sensitivity of vulnerable dugongs to ongoing changes on tropical coastal ecosystems.

Diet and between-tissue isotope comparisons reveal different foraging strategies for age and sex of a Saffron Finch (Sicalis flaveola Linnaeus, 1766) population.

Measuring stable isotopes in different tissues offers the opportunity to provide insight into the foraging ecology of a species. This study aimed to assess how diet varies between yellow females, yellow males, and dull individuals of a Saffron Finch (Sicalis flaveola) population. We measured δ13C and δ15N in blood over a year, and in different feathers, to estimate seasonal consistency of resource use for each category. We conducted this study in a private farm in the Central Brazilian savannas. We sampled 195 individuals in seven field samplings between January 2017 and March 2018. The mean blood δ13C values were similar among yellow females, yellow males and dull individuals, indicating that this population of Saffron Finch predominantly accesses similar resources throughout the year, with a predominant C4 signal. Although Saffron Finch is considered a granivorous species, the mean δ15N values found indicate that both adults and juveniles also incorporate in their tissues some invertebrate. The slight isotope-tissue difference between feathers and blood is similar to the reported in previous studies and may reflect tissue-to-tissue discrimination. The isotopic space of yellow males was greater than that of yellow females and dull individuals, indicating greater dietary diversity due to greater inter-individual variation in diet. In Saffron Finch, which delays plumage maturation, competition-driven partitioning of food resources seems essential in driving carotenoid-based plumage coloration between age classes and sexes.

Hawksbill and green turtle niche overlap in a marine protected area, US Virgin Islands

Studying how species interact with their environment and other co-occurring species are 2 main aspects of ecology. For marine turtles, ocean currents drive migratory routes and may determine the location of surrounding foraging grounds. As a result, circumglobal species like the hawksbill turtle Eretmochelys imbricata and green turtle Chelonia mydas adapt to diverse foraging habitats and employ varied feeding strategies. Dietary specializations may reduce competition for available food and space resources between co-occurring hawksbill and green turtles in US Virgin Island shallow reef habitats. This study analyzed isotopic data from immature hawksbill (n = 49; range: 18.7-49.8 cm straight carapace length [SCL]) and green turtles (n = 225; range: 24.1-69.4 cm SCL) to examine foraging niche. We used nitrogen stable isotope (δ15N) values as an indicator of trophic positioning and carbon stable isotope (δ13C) values as a habitat variable. Turtles were hand-captured across an 8 yr period (2012-2019), which facilitated the distinction of isotopic patterns in both the environment and among individual turtles. Understanding variations in habitat, community dynamics, and dietary consumption allowed us to utilize a 5 point framework to translate isotopic space to foraging niche. We found that the site’s relatively stable environmental conditions allow for isotopic overlap between hawksbill and green turtles despite the specialized feeding strategies each species employs. We also underscore the need to evaluate species-specific tissue turnover estimates as evidenced by the influence of tropical storms on recaptured turtle isotopic signatures. These findings inform our understanding of resource use for these imperiled species at our study site and are useful for future global isotopic comparisons.

A Context for Connectivity: Insights to Environmental Heterogeneity in the Late Pleistocene and Holocene of Southern Africa Through Measuring Isotope Space and Overlap

A Context for Connectivity: Insights to Environmental Heterogeneity in the Late Pleistocene and Holocene of Southern Africa Through Measuring Isotope Space and Overlap

Seasonal recharge mechanism of the upper shallow groundwater in a long-term wastewater leakage and irrigation region of an alluvial aquifer

Understanding the mechanisms that control seasonal groundwater recharge at local and intermediate scales is critical for understanding contaminant transport. The recharge mechanism of seasonal precipitation and irrigation, companied with legacy wastewater in porewater in alluvial aquifer were complicated due to the seasonal variation of multiple recharge sources. In this study, a long-term wastewater leakage and irrigation region along the Tanghe Wastewater Reservoir (TWR) in the alluvial plain area of North China Plain to investigate the recharge mechanism from unsaturated zone to the upper shallow groundwater affected by multiple water sources. Water chemical ions and stable isotopes of water (2H and 18O) of 30 m deep sediment profiles and groundwater boreholes were used to trace the recharge processes. The porewater stable isotopes of the sediment profiles revealed vertical recharge rates ranging from 0.63 to 1.09 m/year for the layered unsaturated zone with silt and silty clay. Due to the matrix flow through unsaturated zone, the legacy wastewater in the unsaturated zone affected the variation of groundwater quality in long term. However, fast flow (i.e., preferential or lateral flow) occurred in sand layers of alluvial aquifers lead to significant precipitation contributions (44 to 61 %) to the upper shallow groundwater (USGW) recharge, resulting in the seasonal variation of stable isotopes and water chemical ions. Affected by the fast flow with seasonal variations and matrix flow with legacy wastewater in the unsaturated zone, the δ2H and δ18O relationship of the USGW showed two types of hysteresis loops in the dual isotope space: 1) groundwater in regions affected by the TWR wastewater leakage shows narrow loops and a nearly straight line with end-members of precipitation that recharged to groundwater by fast flow, and evaporated porewater plotting along the TWR evaporation line; and 2) groundwater in irrigated farmlands with low and high irrigation amounts and intense evaporation shows stronger hysteresis with loops overlapping with shallow porewater, suggesting the impact of legacy wastewater of the unsaturated zone on groundwater. The residual pollutants in soil and the type of fast flow determine the different seasonal variation of groundwater quality. Preferential flow in alluvial aquifer regions can increase the proportion of seasonal recharge from precipitation, resulting in the rapid introduction of contaminants from surface or shallow soils into the alluvial aquifer.

Biological invasions alter the structure of a tropical freshwater food web.

Biological invasions are expected to alter food web structure, but there are limited empirical data directly comparing invaded versus uninvaded food webs, particularly in species-rich, tropical systems. We characterize for the first time the food web of Lake Gatun-a diverse and highly invaded tropical freshwater lake within the Panama Canal. We used stable isotope analysis to reconstruct the trophic structure of the fish community of Lake Gatun and to compare it to that of a minimally invaded reference lake, Lake Bayano. We found significant differences between the trophic structures of these two Neotropical lakes, notably that Lake Gatun's fish community was characterized by a longer food chain, greater isotopic diversity, a broader range of trophic positions and body sizes, and shifts in the isotopic positions of several native taxa relative to Lake Bayano. The degree of isotopic overlap between native and non-native trophic guilds in Lake Gatun was variable, with herbivores exhibiting the lowest (20%-29%) overlap and carnivores the greatest (81%-100%). Overall, our results provide some of the first empirical evidence for the ways in which multiple introduced and native species may partition isotopic space in a species-rich tropical freshwater food web.

Provenance of Aerosol Black Carbon over Northeast Indian Ocean and South China Sea and Implications for Oceanic Black Carbon Cycling.

Aerosol black carbon (BC) is a short-lived climate pollutant. The poorly constrained provenance of tropical marine aerosol BC hinders the mechanistic understanding of extreme climate events and oceanic carbon cycling. Here, we collected PM2.5 samples during research cruise NORC2016-10 through South China Sea (SCS) and Northeast Indian Ocean (NEIO) and measured the dual-carbon isotope compositions (δ13C-Δ14C) of BC using hydrogen pyrolysis technique. Aerosol BC exhibits six different δ13C-Δ14C isotopic spaces (i.e., isotope provinces). Liquid fossil fuel combustion, from shipping emissions and adjacent land, is the predominant source of BC over isotope provinces "SCS close to Chinese Mainland" (53.5%), "Malacca Strait" (53.4%), and "Open NEIO" (40.7%). C3 biomass burning is the major contributor to BC over isotope provinces "NEIO close to Southeast Asia" (55.8%), "Open NEIO" (41.3%), and "Open SCS" (40.0%). Coal combustion and C4 biomass burning show higher contributions to BC over "Sunda Strait" and "Open SCS" than the others. Overall, NEIO near the Bay of Bengal, Malacca Strait, and north SCS are three hot spots of fossil fuel-derived BC; the first two areas are also hot spots of biomass-derived BC. The comparable δ13C-Δ14C between BC in aerosol and dissolved BC in surface seawater may suggest atmospheric BC deposition as a potential source of oceanic dissolved BC.

Peri‐urban systems alter trophic niche size and overlap in sympatric coastal bird species

AbstractUrban habitats can create empty trophic niche space by providing abundant alternative dietary resources, allowing some generalist species to either shift or expand their trophic niches. Resulting changes to trophic niche size may consequently affect interspecific interactions and competition, although trophic impacts are less clear in peri‐urban systems, where both natural and urban resources are readily accessible to highly mobile species. We combined stable isotope (δ13C, δ15N, δ34S) data with GPS tracking of two sympatric coastal bird species (Larus argentatus, L. marinus) across four study sites on the east coast of the United States, ranging from a study site in New York City (the most populous city in the United States) to less‐urban sites off Massachusetts. We quantified the trophic niche size and trophic niche overlap in three‐dimensional isotopic space and assessed spatial overlap in foraging habitat between species at both peri‐urban and less‐urban study sites. We found that for both species, birds at peri‐urban study sites had significantly larger trophic niches than birds from the less‐urban sites. Furthermore, for study sites where both species occurred, we found that overlap in trophic niche space and foraging habitats between species was lower at the peri‐urban study site than at the less‐urban site. These results suggest that peri‐urban environments may facilitate trophic niche expansion and decrease niche overlap in mobile generalist species, contrasting with previous studies showing increased trophic niche overlap in more isolated urban populations. Following further analysis, we found that trophic niche expansion was facilitated by both within‐ and between‐individual differences in foraging strategies. We posit that peri‐urban environments, particularly along coastal areas, can reduce interspecific competition between sympatric species by providing access to a variety of natural and anthropogenic diet items, especially for highly mobile generalist consumers that can access both natural and urban foraging areas. Research assessing how and at what scale peri‐urban systems influence wildlife is key to understanding how further global urbanization will shape ecosystem structures.

Differential effects of clay mineralogy on thermal maturation of sedimentary n-alkanes

Clay minerals serve as important catalysts for the degradation of a range of biomolecules during diagenesis, yet their effects are seldom considered when interpreting organic molecular and isotopic data in the context of paleoenvironmental reconstruction. We investigated the thermal maturation of immature sedimentary organic matter in the presence of two clay minerals (kaolinite and montmorillonite) using a series of laboratory-based anhydrous pyrolysis experiments. Organic matter was extracted from a modern terrestrial sediment, mixed with each clay mineral, and heated at 100–300 °C for up to 30 days – in this way, initial organic matter was identical in each system. Abundances, molecular distributions, and paired compound-specific stable isotopic compositions (δDn-alkane and δ13Cn-alkane) of n-alkanes were measured as a function of heating time. For both kaolinite and montmorillonite amended experiments, the shifts in molecular distributions are highly controlled by significant secondary production of n-alkanes from molecularly large lipid precursors, as evidenced by significant increases in the total amount of n-alkanes accompanying increased thermal maturation. Significant decreases in carbon preference index (CPI) are observed before minor decreases in average chain length (ACL), leading to behavior in CPI-ACL space that is fundamentally different from identical systems free of clay minerals. Furthermore, distinct distributions of secondary n-alkanes between the clay mineral systems indicate differential mechanisms and sites of precursor degradation. In the presence of clay minerals, δ13Cn-alkane of immature bituminous organics initially decreases with increasing thermal maturation, opposite most data reported from experimental alteration of relatively mature sedimentary matter. This shift is similarly driven by secondary production of n-alkanes, arising from kinetic fractionation associated with preferential cleavage of 12C12C bonds from parent molecules – the kinetics of this process vary per clay mineralogy but are controlled by the same process. Conversely, we see an enrichment in δDn-alkane with increasing maturation, indicating control of the two isotopic systems by separate mechanisms. Moreover, kaolinite and montmorillonite exhibit differential control on δDn-alkane, leading to separate domains in dual isotopic space. Overall, the changes in δ13Cn-alkane and δDn-alkane are relatively small over the timescales studied, even at temperatures as high as 300 °C (less than ∼0.6–1‰ for δ13Cn-alkane and ∼8–15‰ for δDn-alkane). Considering these factors on a geological timescale, variations in clay mineralogy through a buried sedimentary sequence may impart matrix effects on molecular and isotopic signatures that can bias interpretation of paleoenvironmental conditions.

Limited evidence for species‐specific sensitivity of temperature‐dependent fractionation of oxygen stable isotope in biominerals: A meta‐analysis

Abstract Water temperature is key to the study of aquatic ectotherm ecology, but precise measurements of individual‐based thermal experience remain difficult to validate. The stable isotope composition of oxygen in biominerals acts as a natural thermometer due to the temperature dependence of isotopic fractionation between water and mineral phases. Coefficients of published temperature‐dependent fractionation equations, however, vary among taxa (the so‐called ‘vital effect’) without apparent consistent predictors, implying that species‐specific experimental validation may be needed before inferring temperature from biomineral oxygen isotope thermometry. Here, we describe a meta‐analysis conducted to assess the influence of biological and experimental sources of variation on the coefficients of published isotope thermometry equations. We observed that the thermal sensitivity (equation slope) was resistant to any biological or experimental factors, while the isotopic spacing between water and biomineral (equation intercept) showed consistent variation. Experimental conditions and phylogeny were the two main sources of variation in equation coefficients, where experiment approaches influenced both equation intercepts and the fit of the linear regression. Our results suggest that the use of common equation slopes and generalized taxa‐specific equation intercepts may be appropriate under some circumstances. We additionally suggest that processes related to oxygen balance and osmoregulation may influence equation intercepts, and suggest further experimental work in this area. Finally, our observations provide ground for improvement for future design and reporting of biomineral thermometry experiments.

Does invasion by armored catfish shift trophic ecology of native fishes? Evidence from stable isotope analysis.

Popular as aquarium fish, armored catfishes from South America (Pterygoplichthys spp.) have been introduced and become invasive in tropical and subtropical regions worldwide. These ecosystem engineers can deplete basal resources (e.g., periphyton and detritus), with potential negative effects for native fauna. We studied the trophic ecology of fishes in the Usumacinta River Basin, Guatemala, where Pterygoplichthys is now widespread and locally abundant. We analyzed stable isotopes (δ13 C, δ15 N) in fish tissues and basal resources to assess the potential impact of Pterygoplichthys on the trophic ecology of six co-occurring native fishes that feed at a similar trophic level (Astyanax aeneus, Dorosoma petenense, Thorichthys pasionis, Oscura heterospila, Poecilia mexicana, and Gambusia sexradiata). The study was conducted during the dry season in the La Pasion (LPR; high invasion) and San Pedro (SPR; low invasion) rivers. We compared isotopic spaces occupied by native fish and Pterygoplichthys, estimated isotopic overlap, and evaluated the trophic displacement of native species. We also evaluated the relationships of environmental factors, including the relative biomass of the invasive catfish, with δ13 C and δ15 N signatures. Except for P. mexicana, native species had lower isotopic overlap with the catfish in LPR. Native fish isotopic spaces were compressed and shifted toward higher trophic positions in LPR relative to SPR. Benthic food resources were important for Pterygoplichthys in both rivers, and water-column resources had greater relative importance (RI) for native species in LPR. Native fish δ13 C was significantly associated with Pterygoplichthys biomass, conductivity, and water flow velocity; and water depth and sedimentation had a significant association with native fish δ15 N. Findings provide evidence that invasive Pterygoplichthys, along with environmental factors, impact the trophic ecology of native fish in the Usumacinta Basin. Additional field research conducted over longer time periods and mesocosm experiments that account for fish assemblage and environmental variation could elucidate Pterygoplichthys impacts via food resource depletion or habitat alteration.