Compound-specific isotopic analysis of amino acids (CSIA-AA) has emerged in the last decade as a powerful approach for tracing the origins and fate of nitrogen in ecological and biogeochemical studies. This approach is based on the empirical knowledge that source AAs (i.e., phenylalanine), fractionate 15 N very little (<0.5‰) during trophic transfer, whereas trophic AAs (i.e., glutamic acid), are greatly (~6-8‰) enriched in 15 N during each trophic step. The differential fractionation of these two AA groups can provide a valuable estimate of consumer trophic position that is internally indexed to the baseline δ 15 N value of the integrated food web. In this paper, we critically review the analytical methods for determining the nitrogen isotopic composition of AAs by gas chromatography/isotope-ratio mass spectrometry. We also discuss methodological considerations for accurate trophic position assessment of organisms using CSIA-AA. We then discuss the advantages and challenges of the CSIA-AA approach by examining published studies including trophic position assessment in various ecosystems, reconstruction of ancient human diets, reconstruction of animal migration and environmental variability, and assessment of marine organic matter dynamics. It is clear that the CSIA-AA approach can provide unique insight into the sources, cycling, and trophic modification of organic nitrogen as it flows through systems. However, some uncertainty still exists in how biochemical, physiological, and ecological mechanisms affect isotopic fractionation of trophic AAs. We end this review with a call for continued exploration of the mechanisms of AA isotopic fractionation, through various studies to promote the evolution of the rapidly growing field of CSIA-AA.

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The oceans are an important global reservoir for mercury (Hg), and marine fish consumption is the dominant human exposure pathway for its toxic methylated form. A more thorough understanding of the global biogeochemical cycle of Hg requires additional information on the mechanisms that control Hg cycling in pelagic marine waters. In this study, Hg isotope ratios and total Hg concentrations are used to explore Hg biogeochemistry in oligotrophic marine environments north of Hawaii. We present the first measurements of the vertical water column distribution of Hg concentrations and the Hg isotopic composition in precipitation, marine particles, and zooplankton near Station ALOHA (22°45′N, 158°W). Our results reveal production and demethylation of methylmercury in both the euphotic (0–175 m) and mesopelagic zones (200–1,000 m). We document a strong relationship between Hg isotopic composition and depth in particles, zooplankton, and fish in the water column and diurnal variations in Δ199Hg values in zooplankton sampled near the surface (25 m). Based on these observations and stable Hg isotope relationships in the marine food web, we suggest that the Hg found in large pelagic fish at Station ALOHA was originally deposited largely by precipitation, transformed into methyl‐Hg, and bioaccumulated in situ in the water column. Our results highlight how Hg isotopic compositions reflect abiotic and biotic production and degradation of methyl‐Hg throughout the water column and the importance of particles and zooplankton in the vertical transport of Hg.

Several studies have found that the respiratory demand for carbon by the mesopelagic community exceeds carbon supply through the particulate sinking flux by up to two to three orders of magnitude, suggesting that mesopelagic communities rely on additional overlooked carbon sources. Suspended particles (defined as 0.7–53 μm) have been suggested as one of these sources but few studies have evaluated their contribution to the mesopelagic food web. We use amino acid compound‐specific nitrogen isotope analysis to investigate whether suspended particles are an important nutritional source to fish, cephalopod, and crustacean micronekton species in the central North Pacific. Our results suggest that micronekton feed from food webs fueled by a variety of nutritional sources including surface dwelling phytoplankton and bacteria, sinking particles, and suspended particles, with micronekton becoming more reliant on suspended particles with increasing habitat depth. Several species were identified as feeding from a primarily suspended particle‐based food web including the fishes Cyema atrum, Cyclothone pallida, Melanocetus johnsonii, Serrivomer sector, and the pelagic octopod Japetella diaphana. We also found that micronekton species feeding from a suspended particle food web cannot be identified using bulk tissue δ15N values. Our data support the notion that suspended particles are an important nutritional source in the lower mesopelagic and upper bathypelagic and they should be accounted for when estimating carbon supply for these communities.

ObjectivesThe Rapa Nui “ecocide” narrative questions whether the prehistoric population caused an avoidable ecological disaster through rapid deforestation and over‐exploitation of natural resources. The objective of this study was to characterize prehistoric human diets to shed light on human adaptability and land use in an island environment with limited resources.Materials and methodsMaterials for this study included human, faunal, and botanical remains from the archaeological sites Anakena and Ahu Tepeu on Rapa Nui, dating from c. 1400 AD to the historic period, and modern reference material. We used bulk carbon and nitrogen isotope analyses and amino acid compound specific isotope analyses (AA‐CSIA) of collagen isolated from prehistoric human and faunal bone, to assess the use of marine versus terrestrial resources and to investigate the underlying baseline values. Similar isotope analyses of archaeological and modern botanical and marine samples were used to characterize the local environment.ResultsResults of carbon and nitrogen AA‐CSIA independently show that around half the protein in diets from the humans measured came from marine sources; markedly higher than previous estimates. We also observed higher δ15N values in human collagen than could be expected from the local environment.DiscussionOur results suggest highly elevated δ15N values could only have come from consumption of crops grown in substantially manipulated soils. These findings strongly suggest that the prehistoric population adapted and exhibited astute environmental awareness in a harsh environment with nutrient poor soils. Our results also have implications for evaluating marine reservoir corrections of radiocarbon dates.

The dynamics of the particulate organic carbon (POC) pool in the ocean are central to the marine carbon cycle. POC is the link between surface primary production, the deep ocean, and sediments. The rate at which POC is degraded in the dark ocean can impact atmospheric CO 2 concentration. Therefore, a central focus of marine organic geochemistry studies is to improve our understanding of POC distribution, composition, and cycling. The last few decades have seen improvements in analytical techniques that have greatly expanded what we can measure, both in terms of organic compound structural diversity and isotopic composition, and complementary molecular omics studies. Here we provide a brief overview of the autochthonous, allochthonous, and anthropogenic components comprising POC in the ocean. In addition, we highlight key needs for future research that will enable us to more effectively connect diverse data sources and link the identity and structural diversity of POC to its sources and transformation processes.

Bacterial hopanoids are ubiquitous in Earth surface environments. They hold promise as environmental and ecological biomarkers, if the phylogeny and physiological drivers of hopanoid biosynthesis can be linked with the distribution of hopanoids observed across a breadth of samples. Here we survey the diversity of hopanoid cyclases from a land-sea gradient across the island of San Salvador, in the easternmost part of the Bahamas. The distribution of lipids was determined for the same sites, for the first time overlaying quantification of bacteriohopanepolyols with sqhC phylogeny. The results are similar to previous reports: environmental sqhCs average < 65% translated amino acid identity to their closest named relatives, and sequences from putative Proteobacteria dominate. Additionally, a new and apparently ubiquitous group of marine hopanoid producers is identified; it has no identifiable close relatives. The greatest diversity of hopanoid lipids occurs in soil, but hopanoids represent a minor fraction of total soil-derived lipids. Marine samples contain fewer identifiable hopanoids, but they are more abundant as a fraction of the total extractable lipids. In soil, the dominant compounds are 35-aminobacteriohopane-32,33,34-triol and adenosylhopane. In an upper estuarine sample, bacteriohopanetetrol and 32,35-anhydrobacteriohopanetetrol dominate; while in lower estuarine and open marine samples, the most abundant are bacteriohopanetetrol and bacteriohopaneribonolactone. Cyclitol ethers are trace components in the soil, absent in the estuary, and of moderate abundance in the open marine setting, suggesting a dominant marine source. Conversely, aminotriol and aminotetrol decrease in abundance or disappear completely from land to ocean, while 2-methyldiplopterol shows the opposite trend. Small quantities of 2-methylbacteriohopanepolyols are detectable in all samples. The overall hopanoid distributions may correlate to the major phylogenetic families of hopanoid producers or to the environments in which they are found.

The goal of the EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) field campaign is to develop a predictive understanding of the export, fate, and carbon cycle impacts of global ocean net primary production. To accomplish this goal, observations of export flux pathways, plankton community composition, food web processes, and optical, physical, and biogeochemical (BGC) properties are needed over a range of ecosystem states. Here we introduce the first EXPORTS field deployment to Ocean Station Papa in the Northeast Pacific Ocean during summer of 2018, providing context for other papers in this special collection. The experiment was conducted with two ships: a Process Ship, focused on ecological rates, BGC fluxes, temporal changes in food web, and BGC and optical properties, that followed an instrumented Lagrangian float; and a Survey Ship that sampled BGC and optical properties in spatial patterns around the Process Ship. An array of autonomous underwater assets provided measurements over a range of spatial and temporal scales, and partnering programs and remote sensing observations provided additional observational context. The oceanographic setting was typical of late-summer conditions at Ocean Station Papa: a shallow mixed layer, strong vertical and weak horizontal gradients in hydrographic properties, sluggish sub-inertial currents, elevated macronutrient concentrations and low phytoplankton abundances. Although nutrient concentrations were consistent with previous observations, mixed layer chlorophyll was lower than typically observed, resulting in a deeper euphotic zone. Analyses of surface layer temperature and salinity found three distinct surface water types, allowing for diagnosis of whether observed changes were spatial or temporal. The 2018 EXPORTS field deployment is among the most comprehensive biological pump studies ever conducted. A second deployment to the North Atlantic Ocean occurred in spring 2021, which will be followed by focused work on data synthesis and modeling using the entire EXPORTS data set.