Compound-specific Stable Isotope Research Articles

Use of Fatty Acids From Aquatic Prey Varies With Foraging Strategy

Across ecosystems, resources vary in their nutritional composition and thus their dietary value to consumers. Animals can either access organic compounds, such as fatty acids, directly from diet or through internal biosynthesis, and the extent to which they use these two alternatives likely varies based on the availability of such compounds across the nutritional landscape. Cross-ecosystem subsidies of important dietary nutrients, like omega-3 long-chain polyunsaturated fatty acids (n-3 LC-PUFA), may provide consumers with the opportunity to relax the demands of synthesis and rely upon dietary flexibility rather than internal metabolic processes. Here, we examined how dietary flexibility and distance from a lake influenced the degree to which generalist insectivores relied upon dietary n-3 LC-PUFA from emergent aquatic insects versus n-3 LC-PUFA synthesized from precursor compounds found in terrestrial insects. We used bulk and compound-specific stable isotope analyses to understand spider and insectivorous bird (Blue Tit;Cyanistes caeruleus) reliance on aquatic and terrestrial resources, including dietary PUFA sources, along a riparian to upland gradient from a lake. We simultaneously investigated n-3 LC-PUFA synthesis ability in nestlings using13C fatty acid labeling. We found that riparian spiders took advantage of emergent aquatic insect subsidies, deriving their overall diet and their n-3 PUFA from aquatic resources whereas nestling birds at all distances and upland spiders relied upon terrestrial resources, including PUFA. Our13C labeling experiment demonstrated that nestling tits were able to synthesize the n-3 LC-PUFA docosahexaenoic acid from the dietary precursor α-linolenic acid, suggesting that they are not limited by aquatic resources to satisfy their LC-PUFA requirements. Overall, this study suggests that habitat generalist insectivores vary in the degree to which they can shift diet to take advantage of high-quality aquatic resources depending upon both their foraging flexibility and internal synthesis capacity.

Compound-specific stable hydrogen isotope (δ2 H) analyses of fatty acids: A new method and perspectives for trophic and movement ecology.

Compound-specific stable isotope analysis (CSIA) is a powerful tool for a better understanding of trophic transfer of dietary molecules in and across ecosystems. Hydrogen isotope values (δ2 H) in consumer tissues have potential to more clearly distinguish dietary sources than 13 C or 15 N values within and among habitats, but have not been used at the fatty acid level for ecological purposes. Here we demonstrate a new online high-capacity gas chromatography-isotope ratio mass spectrometry technique (2 H-CSIA) that offers accurate and reproducible determination of δ2 H values for a range of fatty acids from organisms of aquatic food webs. We show that lipid extracts obtained from aquatic sources, such as biofilms, leaves, invertebrates, or fish muscle tissue, have distinctive δ2 H values that can be used to assess sources and trophic interactions, as well as dietary allocation and origin of fatty acids within consumer tissue. The new 2 H-CSIA method can be applied to evaluate sources and trophic dynamics of fatty acids in organisms ranging from food web ecology to migratory connectivity.

Abyssal deposit feeders are secondary consumers of detritus and rely on nutrition derived from microbial communities in their guts

Trophic ecology of detrital-based food webs is still poorly understood. Abyssal plains depend entirely on detritus and are among the most understudied ecosystems, with deposit feeders dominating megafaunal communities. We used compound-specific stable isotope ratios of amino acids (CSIA-AA) to estimate the trophic position of three abundant species of deposit feeders collected from the abyssal plain of the Northeast Pacific (Station M; ~ 4000 m depth), and compared it to the trophic position of their gut contents and the surrounding sediments. Our results suggest that detritus forms the base of the food web and gut contents of deposit feeders have a trophic position consistent with primary consumers and are largely composed of a living biomass of heterotrophic prokaryotes. Subsequently, deposit feeders are a trophic level above their gut contents making them secondary consumers of detritus on the abyssal plain. Based on δ13C values of essential amino acids, we found that gut contents of deposit feeders are distinct from the surrounding surface detritus and form a unique food source, which was assimilated by the deposit feeders primarily in periods of low food supply. Overall, our results show that the guts of deposit feeders constitute hotspots of organic matter on the abyssal plain that occupy one trophic level above detritus, increasing the food-chain length in this detritus-based ecosystem.

Fatty acid accumulation in feeding types of a natural freshwater fish population

Fatty acids are widely used to study trophic interactions in food web assemblages. Generally, it is assumed that there is a very small modification of fatty acids from one trophic step to another, making them suitable as trophic biomarkers. However, recent literature provides evidence that many fishes possess genes encoding enzymes with a role in bioconversion, thus the capability for bioconversion might be more widespread than previously assumed. Nonetheless, empirical evidence for biosynthesis occurring in natural populations remains scarce. In this study, we investigated different feeding types of perch (Perca fluviatilis) that are specialized on specific resources with different levels of highly unsaturated fatty acids (HUFAs), and analyzed the change between HUFA proportions in perch muscle tissue compared to their resources. Perch showed matching levels to their resources for EPA, but ARA and especially DHA were accumulated. Compound-specific stable isotope analyses helped us to identify the origin of HUFA carbon. Our results suggest that perch obtain a substantial amount of DHA via bioconversion when feeding on DHA-poor benthic resources. Thus, our data indicate the capability of bioconversion of HUFAs in a natural freshwater fish population.

Novel Applications of Technology for Advancing Tidal Marsh Ecology

Over the last 20 years, innovations have led to the development of exciting new technologies and novel applications of established technologies, collectively increasing the scale, scope, and quality of research possible in tidal marsh systems. Thus, ecological research on marshes is being revolutionized, in the same way as ecological research more generally, by the availability of new tools and analytical techniques. This perspective highlights current and potential applications of novel research technologies for marsh ecology. These are summarized under several themes: (1.) imagery — sophisticated imaging sensors mounted on satellites, drones, and underwater vehicles; (2.) animal tracking — acoustic telemetry, passive integrated transponder (PIT) tags, and satellite tracking, and (3.) biotracers — investigation of energy pathways and food web structure using chemical tracers such as compound-specific stable isotopes, isotope addition experiments, contaminant analysis, and eDNA. While the adoption of these technological advances has greatly enhanced our ability to examine contemporary questions in tidal marsh ecology, these applications also create significant challenges with the accessibility, processing, and synthesis of the large amounts of data generated. Implementation of open science practices has allowed for greater access to data. Newly available machine learning algorithms have been widely applied to resolve the challenge of detecting patterns in massive environmental datasets. The potential integration on digital platforms of multiple, large data streams measuring physical and biological components of tidal marsh ecosystems is an opportunity to advance science support for management responses needed in a rapidly changing coastal landscape.

Algal blooms modulate organic matter remineralization in freshwater sediments: A new insight on priming effect

This study provides a novel insight into the degradation of sediment organic matter (SOM) regulated by algae-derived organic matter (AOM) based on priming effect. We tracked the dynamics of SOM mineralization products and pathways, together with priming effects (PE) using the compound-specific stable isotope (δ13C) technique following addition of low- and high-density algal debris in sediments. We found that algal debris increased the total carbon oxidation rate, and resulted in denitrification and methanogenesis-dominated SOM mineralization. While iron reduction and sulphate reduction played important roles in the early period of algal accumulation. Total carbon oxidation rate and anaerobic rates (Ranaerobic) were higher in the amended treatments compared with that in the control. Analysis indicated that algal debris had a positive PE on SOM mineralization, which caused an intensified mineralization in the initial phase with over 80% of dissolved inorganic carbon deriving from SOM degradation. Total carbon oxidation rate of SOM deduced from priming effect (RTCOR-PE) was similar to Ranaerobic, further indicating SOM mineralization was a critical source of the end products. These findings deviate the causal focus from the decomposition of AOM, and confirm the accumulation of AOM as the facilitator of SOM mineralization. Our study offers empirical evidences to advance the traditional view on the effect of AOM on SOM mineralization.

Detection of exogenous sugars in pineapple juice using compound-specific stable hydrogen isotope analysis

An improved procedure for determining 2H/1H isotope ratios, using gas chromatography-isotope ratio mass spectrometry, has been used to detect the addition of exogenous C4-plant-derived sugars to pineapple juice. Isotopic techniques are commonly used to identify the addition of low-cost sugars to fruit juices and are difficult to subvert as it is not economically viable to change the isotopic ratios of the sugars. However, the addition of cane sugar to pineapple juice has presented a significant challenge that is only detected by site-specific 13C analysis of the methyl and methylene positions of ethanol derived from pineapple sugars, measured by nuclear magnetic resonance. This new GC-IRMS-based procedure utilises the trifluoroacetate derivative of sucrose to allow direct measurement of the carbon-bound non-exchangeable hydrogen. This provides advantages over alternative isotopic methods in terms of analysis time and sensitivity. This feasibility study has demonstrated the potential to reliably differentiate between authentic pineapple juices and those adulterated with commercial beet and cane sucrose.

Interactions at surface-subterranean ecotones: structure and function of food webs within spring orifices.

Spring orifices are ecotones between surface and subterranean aquatic ecosystems. Invertebrates of different origins (e.g., surface, spring obligate, and subterranean) coexist in these spatially restricted environments, potentially competing for resources. However, processes that allow for population coexistence in these presumably low resource environments are not well understood. We examined invertebrate communities at two spring complexes in Texas, USA and assessed resource use and food web structure at spring orifices using stable isotopes of carbon (δ13C) and nitrogen (δ15N). Using bulk δ13C and δ15N of organisms and potential food sources, we elucidated dietary sources and found that invertebrate communities exhibited resource partitioning and contained two main food chains (periphyton versus terrestrial organic matter [OM]). In both spring complexes, several endemic spring orifice associated and subterranean taxa derived most of their diet from terrestrial OM. Analysis of compound-specific stable isotopes (i.e., δ13C of essential amino acids, EAAs) from two co-occurring elmid species indicated that the endemic spring orifice-associated species (Heterelmis comalensis) derived > 80% of its EAAs from bacteria, whereas the widespread surface species (Microcylloepus pusillus) derived its EAAs from a more equitable mix of bacteria, fungi, and algae. We additionally calculated niche overlap among of several taxonomically related groups (aquatic beetles and amphipods) that co-occur in spring ecotones and posterior probability estimates indicated little to no niche overlap among related species. Results indicate that invertebrates at subterranean-surface aquatic ecotones are partitioning food resources and highlight the importance of connections to riparian zones for persistence of several endemic invertebrates.

Amino acid δ15N differences consistent with killer whale ecotypes in the Arctic and Northwest Atlantic.

Ecotypes are groups within a species with different ecological adaptations than their conspecifics. Eastern North Pacific (ENP) killer whale (Orcinus orca) ecotypes differ in their diet, behavior, and morphology, but the same is not known for this species in the eastern Canadian Arctic (ECA) and Northwest Atlantic (NWA). Using compound-specific stable isotope analysis (CSIA) of amino acids (AAs), we compared δ15N patterns of the primary trophic and source AA pair, glutamic acid/glutamine (Glx) and phenylalanine (Phe), in dentine collagen of (1) sympatric ENP killer whale ecotypes with well-characterized diet differences and (2) ECA/NWA killer whales with unknown diets. δ15NGlx-Phe was significantly higher in the ENP fish-eating (FE) than mammal-eating (ME) ecotype (19.2 ± 0.4‰ vs. 13.5 ± 0.7‰, respectively). Similar bimodal variation in δ15NGlx-Phe indicated analogous dietary divisions among ECA/NWA killer whales, with two killer whales having higher δ15NGlx-Phe (16.5 ± 0.0‰) than the others (13.5 ± 0.6‰). Inferences of dietary divisions between these killer whales were supported by parallel differences in threonine δ15N (–33.5 ± 1.6‰ and –40.4 ± 1.1‰, respectively), given the negative correlation between δ15NThr and TP across a range of marine consumers. CSIA-AA results for ECA/NWA whales, coupled with differences in tooth wear (a correlate for diet), are consistent with ecotype characteristics reported in ENP and other killer whale populations, thus adding to documented ecological divergence in this species worldwide.

Legacy of historic land cover changes on sediment provenance tracked with isotopic tracers in a Mediterranean agroforestry catchment

A Compound Specific Stable Isotope (CSSI) sediment tracing approach is applied for the first time in a Mediterranean mountain agroforestry catchment subjected to intense land use changes in the past decades. Many Mediterranean mountain environments underwent conversion of rangelands into croplands during the previous centuries to increase agricultural production. Converted land has increased the risk of erosion and in some cases has led to loss of the entire fertile topsoil. After land abandonment the process was gradually reversed during the middle of the 20th century, allowing the recovery of natural land cover and reduction of soil erosion rates.The 13C abundance of long chain fatty acids was used as tracer to assess the contribution of soil under different vegetation covers in complex landscapes subjected to land use changes after land abandonment in a medium-sized Mediterranean catchment. A Bayesian mixing model (MixSIAR) was used for estimating the contribution of different land use types to suspended sediments. To this purpose, composite samples were collected over the four main land covers existing in the study area: cropland, Mediterranean forest, pine forest, scrubland, and two main geomorphic elements: highly disturbed areas such as exposed subsoil and channel banks. Suspended sediment traps were installed at three locations in the catchment to assess the variability of source contributions from the headwaters to the outlet of the catchment. At every sampling point three replicating traps integrated the suspended sediment per climatologic season during a one hydrological year. The fatty acids (FAs) content was significantly higher at the catchment outlet than at the headwaters. The δ13C signatures of the FAs were successful in discriminating between Mediterranean forest, scrubland, pine forest and both geomorphic elements. Overall, the model identified agricultural land as the largest contributing source for most of the sampled seasons. The inclusion of prior information with different informativeness produced variations in the model outputs and could represent an advantage as much as a disadvantage if priors are not used with caution and supported by robust evidence. The results of this study suggest that CSSI tracers are needed to correctly assess land use related sediment sources, while channel bank and subsoil contributions require geochemical tracers. The high agricultural apportionment despite its small coverage (16%) point out to the impact of human activities and the agriculture cycle on soil loss in these mountain agroforestry systems.

Multi-element (13C, 2H and 34S) bulk and compound-specific stable isotope analysis for authentication of Allium species essential oils

Pure and natural essential oils of Allium species are primarily used in the food industry, but due to their low yield, production quantities can be difficult to achieve and thus can be highly expensive. Due to these problems, adulterations are a reality in this field. The purpose of this research is to develop a multi element stable isotope analysis methodology for authentication of the essential oils of leek, onion, shallot, and chive. Naturalness of these essential oils was achieved by assessment of compound specific δ13C and δ34S: an addition of 5% of synthetic compound can be detected. Chemometric models were undertaken to assess purity by distinction of the Allium samples according to their species origin using bulk stable and compound specific δ13C, δ2H, δ34S, and compositions of their major metabolites dipropyl disulfide, dipropyl trisulfide, methyl propyl disulfide, and methyl propyl trisulfide.

Geochemical evidence for fugitive gas contamination and associated water quality changes in drinking-water wells from Parker County, Texas.

Extensive development of horizontal drilling and hydraulic fracturing enhanced energy production but raised concerns about drinking-water quality in areas of shale-gas development. One particularly controversial case that has received significant public and scientific attention involves possible contamination of groundwater in the Trinity Aquifer in Parker County, Texas. Despite extensive work, the origin of natural gas in the Trinity Aquifer within this study area is an ongoing debate. Here, we present a comprehensive geochemical dataset collected across three sampling campaigns along with integration of previously published data. Data include major and trace ions, molecular gas compositions, compound-specific stable isotopes of hydrocarbons (δ13C-CH4, δ13C-C2H6, δ2H-CH4), dissolved inorganic carbon (δ13C-DIC), nitrogen (δ15N-N2), water (δ18O, δ2H, 3H), and noble gases (He, Ne, Ar), boron (δ11B) and strontium (87Sr/86Sr) isotopic compositions of water samples from 20 drinking-water wells from the Trinity Aquifer. The compendium of data confirms mixing between a deep, naturally occurring salt- (Cl >250mg/L) and hydrocarbon-rich groundwater with a low-salinity, shallower, and younger groundwater. Hydrocarbon gases display strong evidence for sulfate reduction-paired oxidation, in some cases followed by secondary methanogenesis. A subset of drinking-water wells contains elevated levels of hydrocarbons and depleted atmospherically-derived gas tracers, which is consistent with the introduction of fugitive thermogenic gas. We suggest that gas originating from the intermediate-depth Strawn Group ("Strawn") is flowing along the annulus of a Barnett Shale gas well, and is subsequently entering the shallow aquifer system. This interpretation is supported by the expansion in the number of affected drinking-water wells during our study period and the persistence of hydrocarbon levels over time. Our data suggest post-genetic secondary water quality changes occur following fugitive gas contamination, including sulfate reduction paired with hydrocarbon oxidation and secondary methanogenesis. Importantly, no evidence for upward migration of brine or natural gas associated with the Barnett Shale was identified.

Evaluation of a quick one-step sample preparation method for the determination of the isotopic fingerprint of rapeseed (Brassica napus): Investigation of the influence of the use of 2,2-dimethoxypropane on compound-specific stable carbon and hydrogen isotope analyses by gas chromatography combustion/pyrolysis isotope ratio mass spectrometry.

Gas chromatographic analyses for vegetable oils require transesterification, which generally involves multiple steps, mainly to generate fatty acid methyl esters (FAMEs). A quick method based on acid-catalyzed transesterification using 2,2-dimethoxypropane (DMP) enables the conversion in one step, in a single reactor. For compound-specific stable carbon and hydrogen isotope analyses (C- and H-CSIA) of individual fatty acids (FAs) in oil, the verification of this one-step method has not yet been reported. In this study, we evaluated the feasibility of the one-step method for C- and H-CSIA of individual FAMEs in rapeseed samples. The focus was on the investigation of the influence of methanol, which was produced from the reactions of DMP with glycerol and water during transesterification, on the accuracy of isotope composition of FAMEs, consequently of the FAs. The reproducibility of the one-step method was assessed by the measurement of the FAMEs from rapeseed and rapeseed oil. For the C- and H-CSIA of individual FAMEs, a gas chromatography combustion/pyrolysis isotope ratio mass spectrometry system was used. Our results showed that no significant differences arise in the carbon and hydrogen isotope compositions of the selected main FAMEs produced with and without DMP except for the H-CSIA value of C18:3. The reproducibility of the one-step method for rapeseed was in the range of ±0.1 mUr to ± 0.3 mUr for C-CSIA and ±1 mUr to ±3 mUr for H-CSIA of the main FAMEs. DMP improves the transesterification efficiency without influencing the accuracy of the C- and H-CSIA of FAMEs. The performance of the one-step method for rapeseed samples for the determination of C- and H-CSIA values of FAMEs is satisfactory. Thus, the applicability of the one-step method for isotopic fingerprint analyses of FAs in oilseeds is reported for the first time.

Assessment of chlorinated ethenes degradation after field scale injection of activated carbon and bioamendments: Application of isotopic and microbial analyses

Over the last decade, activated carbon amendments have successfully been applied to retain chlorinated ethene subsurface contamination. The concept of this remediation technology is that activated carbon and bioamendments are injected into aquifer systems to enhance biodegradation. While the scientific basis of the technology is established, there is a need for methods to characterise and quantify the biodegradation at field scale. In this study, an integrated approach was applied to assess in situ biodegradation after the establishment of a cross sectional treatment zone in a TCE plume. The amendments were liquid activated carbon, hydrogen release donors and a Dehalococcoides containing culture. The integrated approach included spatial and temporal evaluations on flow and transport, redox conditions, contaminant concentrations, biomarker abundance and compound-specific stable isotopes. This is the first study applying isotopic and microbial techniques to assess field scale biodegradation enhanced by liquid activated carbon and bioamendments. The injection enhanced biodegradation from TCE to primarily cis-DCE. The Dehalococcoides abundances facilitated characterisation of critical zones with insufficient degradation and possible explanations. A conceptual model of isotopic data together with distribution and transport information improved process understanding; the degradation of TCE was insufficient to counteract the contaminant input by inflow into the treatment zone and desorption from the sediment. The integrated approach could be used to document and characterise the in situ degradation, and the isotopic and microbial data provided process understanding that could not have been gathered from conventional monitoring tools. However, quantification of degradation through isotope data was restricted for TCE due to isotope masking effects. The combination of various monitoring tools, applied frequently at high-resolution, with system understanding, was essential for the assessment of biodegradation in the complex, non-stationary system. Furthermore, the investigations revealed prospects for future research, which should focus on monitoring contaminant fate and microbial distribution on the sediment and the activated carbon.

Compound-Specific Chlorine Isotope Analysis of Organochlorine Pesticides by Gas Chromatography-Negative Chemical Ionization Mass Spectrometry.

Compound-specific stable chlorine isotope analysis (CSIA-Cl) is an important method for identifying sources of organochlorine contaminants and helping assess their quantification of transformation processes. However, the present CSIA-Cl is challenged by either redundant conversion pretreatment or complicated mathematical correction. To overcome the mentioned problems, a novel method has been developed for the CSIA-Cl of eight organochlorine pesticides using gas chromatography-negative chemical ionization mass spectrometry (GC-NCI-qMS) in this study. The instrument parameters, acquisition mode, and required injection amounts were optimized in terms of the precision of GC-NCI-qMS. An ionization energy of 90 eV and emission current of 90 μA were selected, and the precisions for eight organochlorine pesticides were in the range of 0.37‰–2.15‰ in single ion monitoring (SIM) mode when the injected amount was 0.50 mg L−1 (viz. 0.5 ng on column). Furthermore, when standards from Supelco and O2si were calibrated using standards from AccuStandard regarded as external isotope standard, chlorine isotope composition of α-hexachlorocyclohexane (α-HCH) and 2, 2-dichloro−1, 1-bis (4-chlorophenyl) ethylene (p, p′-DDE) in Supelco and O2si was confidently differentiated. The provenance identification method was validated by three organochlorine contaminated groundwater samples and showed a prospect in identifying the source of organochlorine pesticides.

Competitive microbial degradation among PBDE congeners in anaerobic wetland sediments: Implication by multiple-line evidences including compound-specific stable isotope analysis

Polybrominated diphenyl ethers (PBDEs) are widespread contaminants in the environment. Microbial reductive debromination is one of the important attenuation processes for PBDEs in the anaerobic sediments. This study first investigated the interaction between BDE-47 and BDE-153 during the microbial degradation in wetland sediments by the multiple-line approaches including biodegradation kinetics, microbial community structures and stable isotope composition. BDE-47 and BDE-153 biodegradation fitted pseudo-zero-order kinetics, with the higher degradation rates in single than combined exposure, indicating the mutual inhibition in co-exposure condition. BDE-47 and BDE-153 shared the common dehalogenators (genus Dehalococcoides and Acinetobacter) with enrichment in combined exposure, indicating the potential competition in dehalogenating bacteria during biodegradation. Microbial degradation could lead to the isotopic fractionation of BDE-47 and BDE-153, with the smaller changes in δ13C in combined than single exposure. The apparent kinetic isotope effect of carbon (AKIEC) was different between BDE-47 and BDE-153 in single exposure, whilst identical in combined exposure, indicating the similar degradation mechanism for BDE-47 and BDE-153 in co-exposure condition. These results revealed that the competition on microbial degradation occurred among PBDEs in co-exposure condition, which was important for the comprehensive risk assessment of simultaneous exposure to multiple PBDE congeners in the environment.

Electrochemical degradation of atrazine by BDD anode: Evidence from compound-specific stable isotope analysis and DFT simulations

Direct charge transfer (DCT) and •OH attack played important roles in contaminant degradation by BDD electrochemical oxidation. Their separate contributions and potential bond-cleavage processes were required but lacking. Here, we carried out promising compound-specific isotope fractionation analysis (CSIA) to explore 13C and 2H isotope fractionation of atrazine (ATZ), followed by assessing the reaction pathway by BDD anode. The correlation of 2H and 13C fractionation allows to remarkably differentiate DCT process and •OH attack, with Λ values of 18.99 and 53.60, respectively. Radical quenching identified that •OH accounted for 79.0%–88.5% in the whole reaction. While CSIA methods provided biased results, which suggested that ATZ degradation exhibited two stages with •OH contributions of 24.6% and 84.3% respectively, confirming CSIA was more sensitive and provided more possibilities to estimate degradation processes. Combined with Fukui index and intermediate products identification, we deduced that dechlorination-hydroxylation mainly occurred in the first 30 min by DCT reaction. While lateral chain oxidation with C–N broken was the governing route once •OH was largely generated, with the production of DEA (m/z 188), DIA (m/z 174), DEIA (m/z 146) and DEIHA (m/z 128). Our results demonstrated that isotope fractionation can offer “isotopic footprints” for identifying the rate-limiting steps and bond breakage process, and opens new avenues for degradation pathways of contaminants.

Influence of Species-Specific Feeding Ecology on Mercury Concentrations in Seabirds Breeding on the Chatham Islands, New Zealand.

Mercury (Hg) is a toxic metal that accumulates in organisms and biomagnifies along food webs; hence, long-lived predators such as seabirds are at risk as a result of high Hg bioaccumulation. Seabirds have been widely used to monitor the contamination of marine ecosystems. In the present study, we investigated Hg concentrations in blood, muscle, and feathers of 7 procellariform seabirds breeding on the Chatham Islands, New Zealand. Using bulk and compound-specific stable isotope ratios of carbon and nitrogen as a proxy of trophic position and distribution, we also tested whether Hg contamination is related to the species-specific feeding ecology. Mercury exposure varied widely within the seabird community. The highest contaminated species, the Magenta petrel, had approximately 29 times more Hg in its blood than the broad-billed prion, and approximately 35 times more Hg in its feathers than the grey-backed storm petrel. Variations of Hg concentrations in blood and feathers were significantly and positively linked to feeding habitats and trophic position, highlighting the occurrence of efficient Hg biomagnification processes along the food web. Species and feeding habitats were the 2 main drivers of Hg exposure within the seabird community. The Pterodroma species had high blood and feather Hg concentrations, which can be caused by their specific physiology and/or because of their foraging behavior during the interbreeding period (i.e., from the Tasman Sea to the Humboldt Current system). These 2 threatened species are at risk of suffering detrimental effects from Hg contamination and further studies are required to investigate potential negative impacts, especially on their reproduction capability. Environ Toxicol Chem 2021;40:454-472. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Synthesis and release of fatty acids under the interaction of Ulva pertusa and Heterosigma akashiwo by stable isotope analysis

Symbiosis of marine algae is inevitable in the marine environment, and species may occur interaction on the growth. In this study, the macroalgae Ulva pertusa and marine microalgae Heterosigma akashiwo were selected as target species to study the interaction mechanism between them. After the 8 days of co-cultivation, the inhibition on growth was observed for both of U. pertusa and H. akashiwo. Eight fatty acids in U. pertusa was detected, with the significant decrease in contents of polyunsaturated fatty acids (PUFAs) especially for C18:2, C18:3n-3 and C18:3n-6. Twelve fatty acids in H. akashiwo was detected, with the significant change for PUFAs. PUFA concentrations in the co-culture group were less than those in the mono-culture. Meanwhile the principal component analysis was conducted to insight into the interaction between U. pertusa and H. akashiwo by fatty acids content and carbon stable isotope ratio of fatty acids (δ13CFAs). Fatty acid content could not distinguish mono and co-culture. However, δ13CFAs could distinguish not only the culture time of algae, but also the living environment of algae. In addition, this study combined fatty acids content and δ13CFAs to explore the release of fatty acids by algae into the seawater. The C18:3n-3 was identified as the allelochemical released by U. pertusa to inhibit the growth of H. akashiwo. The ratio of δ13CFAs in seawater decreased. This study provides a theoretical basis for the symbiosis of marine algae, and a new method of compound-specific stable carbon isotopes was used to better explore the metabolism of fatty acids in algae.

Amino acid δ13C and δ15N patterns from sediment trap time series and deep-sea corals: Implications for biogeochemical and ecological reconstructions in paleoarchives

Recent work using compound-specific stable isotopes of amino acids (CSI-AA) in proteinaceous deep-sea corals opens a new realm of high-fidelity reconstruction for biogeochemical and ecological changes in the ocean. However, underlying these CSI-AA paleoceanographic applications are a series of fundamental assumptions, which hold first that baseline-proxy AA isotope values fixed at the base of food webs represent integrated δ13C and δ15N values of primary production, and second they are unaltered during subsequent export and incorporation from particles into corals. We explored long-term δ13C and δ15N CSI-AA data on a sediment trap time series together with contemporaneous, geographically close deep-sea bamboo corals (Isidella sp.) in the California margin, directly testing these assumptions for the first time. Our data show that isotope values of essential (δ13CEAA) and source AAs (δ15NPhe) in sinking particles quantitatively track bulk δ13C and δ15N values of export production. These CSI-AA baseline proxies varied independently of carbon flux, trophic position (TPCSI-AA) and microbial alteration, suggesting that they were well preserved in the sinking particles consumed by corals. Paired comparisons between sinking particles and corals revealed minor elevations of δ13CEAA (by ∼2‰) and δ15NPhe (by ∼1‰) in available coral specimens. We hypothesize that the difference in δ13CEAA is due to the geographic offset in δ13C values of primary production expected between the (more offshore) sediment trap site and (more onshore) coral specimens, whereas the δ15NPhe offset is likely related to expected minor trophic fractionation. Using empirical models derived from the sediment trap time series, we demonstrate for the first time that CSI-AA in proteinaceous deep-sea corals can reconstruct known bulk δ15N values of export production, source nitrogen δ15N values, and exported TPCSI-AA values with very good fidelity. Together, these findings represent a major advance in our understanding of AA isotope behavior in modern and paleoarchives, and can be used to underpin the rapidly evolving use of CSI-AA-based tools in multiple paleoceanographic studies and archives.