Biomagnification of mercury in an estuarine food web.

Methylmercury is a toxin of local, regional, and global concern, with estuarine habitats possessing ecological characteristics that support conversion of inorganic mercury into this methylated form. We monitored Hg concentrations in species within the food web of the lower Cape Fear River (CFR) estuary in 2018-2020. Samples were analyzed for Hg concentrations and nitrogen isotopes (a measure of trophic level), and we found a positive relationship within this food web each year (p < 0.0001), indicating biomagnification is occurring. The highest Hg concentrations were among the upper trophic level species (Royal Terns, 4.300 ppm). While the Hg concentrations we documented are below assumed thresholds for toxic effects, we found spikes in Hg concentrations after Hurricane Florence in 2018 and with other disturbances to the CFR that resuspended bottom sediments. Continued monitoring is needed to understand the cause of annual variations, health implications, and conservation needs.

Molecular transformation of organic nitrogen in Antarctic penguin guano-affected soil.

Organic nitrogen (ON) is an important participant in the Earth's N cycle. Previous studies have shown that penguin feces add an abundance of nutrients including N to the soil, significantly changing the eco-environment in ice-free areas in Antarctica. To explore the molecular transformation of ON in penguin guano-affected soil, we collected guano-free weathered soil, modern guano-affected soil from penguin colonies, ancient guano-affected soil from abandoned penguin colonies, and penguin feces from the Ross Sea region, Antarctica, and Fourier transform ion cyclotron mass spectrometry (FT-ICR MS) was used to investigate the chemical composition of water-extractable ON. By comparing the molecular compositions of ON among different samples, we found that the number of ON compounds (>4,000) in weathered soil is minimal, while carboxylic-rich alicyclic-like molecules (CRAM-like) are dominant. Penguin feces adds ON into the soil with > 10,000 CHON, CHONS and CHN compounds, including CRAM-like, lipid-like, aliphatic/ peptide-like molecules and amines in the guano-affected soil. After the input of penguin feces, macromolecules continue to degrade, and other ON compounds tend to be oxidized into relatively stable CRAM-like molecules, this is an important transformation process of ON in guano-affected soils. We conclude the roles of various forms of ON in the N cycle are complex and diverse. Combined with previous studies, ON eventually turns into inorganic N and is lost from the soil. The lost N ultimately returns to the ocean and the food web, thus completing the N cycle. Our study preliminarily reveals the molecular transformation of ON in penguin guano-affected soil and is important for understanding the N cycle in Antarctica.

Elevated Mercury Concentrations and Isotope Signatures (N, C, Hg) in Yellowfin Tuna (Thunnus albacares) from the Galápagos Marine Reserve and Waters off Ecuador.

We examined how dietary factors recorded by C and N influence Hg uptake in 347 individuals of yellowfin tuna (Thunnus albacares), an important subsistence resource from the Galápagos Marine Reserve (Ecuador) and the Ecuadorian mainland coast in 2015-2016. We found no differences in total Hg (THg) measured in red muscle between the two regions and no seasonal differences, likely due to the age of the fish and slow elimination rates of Hg. Our THg concentrations are comparable to those of other studies in the Pacific (0.20-9.60 mg/kg wet wt), but a subset of individuals exhibited the highest Hg concentrations yet reported in yellowfin tuna. Mercury isotope values differed between Δ199 Hg and δ202Hg in both regions (Δ199 Hg = 2.86 ± 0.04‰ vs. Δ199 Hg = 2.33 ± 0.07‰), likely related to shifting food webs and differing photochemical processing of Hg prior to entry into the food web. There were significantly lower values of both δ15 N and δ13 C in tuna from Galápagos Marine Reserve (δ15 N: 8.5-14.2‰, δ13 C: -18.5 to -16.1‰) compared with those from the Ecuadorian mainland coast (δ15 N: 8.3-14.4‰, δ13 C: -19.4 to -11.9‰), of which δ13 C values suggest spatially constrained movements of tuna. Results from the pooled analysis, without considering region, indicated that variations in δ13 C and δ15 N values tracked changes of Hg stable isotopes. Our data indicate that the individual tuna we used were resident fish of each region and were heavily influenced by upwellings related to the eastern Pacific oxygen minimum zone and the Humboldt Current System. The isotopes C, N, and Hg reflect foraging behavior mainly on epipelagic prey in shallow waters and that food web shifts drive Hg variations between these populations of tuna. Environ Toxicol Chem 2022;41:2732-2744. © 2022 SETAC.

A 14,000-year-old genome sheds light on the evolution and extinction of a Pleistocene vulture.

The New World Vulture [Coragyps] occidentalis (L. Miller, 1909) is one of many species that were extinct by the end of the Pleistocene. To understand its evolutionary history we sequenced the genome of a 14,000 year old [Coragyps] occidentalis found associated with megaherbivores in the Peruvian Andes. occidentalis has been viewed as the ancestor, or possibly sister, to the extant Black Vulture Coragyps atratus, but genomic data shows occidentalis to be deeply nested within the South American clade of atratus. Coragyps atratus inhabits lowlands, but the fossil record indicates that occidentalis mostly occupied high elevations. Our results suggest that occidentalis evolved from a population of atratus in southwestern South America that colonized the High Andes 300 to 400 kya. The morphological and morphometric differences between occidentalis and atratus may thus be explained by ecological diversification following from the natural selection imposed by this new and extreme, high elevation environment. The sudden evolution of a population with significantly larger body size and different anatomical proportions than atratus thus constitutes an example of punctuated evolution.

At the beginnings of the funerary Megalithism in Iberia at Campo de Hockey necropolis.

The excavations undertaken at the Campo de Hockey site in 2008 led to the identification of a major Neolithic necropolis in the former Island of San Fernando (Bay of Cádiz). This work presents the results of the latest studies, which indicate that the site stands as one of the oldest megalithic necropolises in the Iberian Peninsula. The main aim of this work is to present with precision the chronology of this necropolis through a Bayesian statistical model that confirms that the necropolis was in use from c. 4300 to 3800 cal BC. The presence of prestige grave goods in the earliest and most monumental graves suggest that the Megalithism phenomenon emerged in relation to maritime routes linked to the distribution of exotic products. We also aim to examine funerary practices in these early megalithic communities, and especially their way of life and the social reproduction system. As such, in addition to the chronological information and the Bayesian statistics, we provide the results of a comprehensive interdisciplinary study, including anthropological, archaeometric and genetic data.

Fraction distribution and dynamic cycling of phosphorus in lacustrine sediment at Inexpressible Island, Antarctica.

Phosphorus (P) chemistry and its dynamic cycling are essential for understanding aquatic primary productivity and ecosystem structure. However, there is a lack of knowledge on P chemistry in pristine aquatic ecosystems, such as in Antarctica. Here, we applied the Standards, Measurements and Testing Program (SMT) procedure and nuclear magnetic resonance spectroscopy (NMR) to reveal P speciation in two types of lacustrine sediment cores collected from Inexpressible Island, Ross Sea, East Antarctica. The Positive Matrix Factorization Model and Generalized Additive Models were applied to quantitatively identify the P sources and estimate relative effects of various environmental factors on the speciation. Our results demonstrate that orthophosphate, mainly as Ca-P, is the major component and the ortho-monoesters are the predominant organic phosphorus (OP) form in lacustrine sediments. Ornithogenic lacustrine sediments have a higher content of P as Ca-P than sediments with little or no penguin influence. Our model further suggests that penguin guano is the most important source for Ca-P, accounting for 80%, while detrital input is the predominant source for Fe/Al-P (up to 90%). The content of ortho-monoesters, as revealed by NMR, declines with depth, reflecting mineralization process of OP in the sediments. Moreover, we observed higher relative proportions of organic P in the sediments with little guano influence and the deposition of organic P are likely facilitated by microbial mats. Overall, our data suggest that burial of P in Antarctic lakes is sensitive to different P sources and sedimentary environments. The relatively higher bioavailable phosphorus in lacustrine sediments largely controls growth of aquatic microbial mats in oligotrophic lakes and ponds in Antarctica. The sediment profile data also indicate that P burial increased during the Medieval Climate Anomaly period, and climate warming is more conducive to P burial through the expansion of penguin populations and productivity of microbial mats. Our findings represent the first systematic understanding of natural P cycling dynamics and its main controlling factors in pristine ponds with different organic sources in Antarctica.

Intraspecific Variation in Mercury, δ15 N, and δ13 C Among 3 Adélie Penguin (Pygoscelis adeliae) Populations in the Northern Antarctic Peninsula Region.

Mercury (Hg) is a pervasive environmental contaminant that accumulates in the organs and tissues of seabirds at concentrations capable of causing acute or long-term adverse health effects. In the present study, Hg concentrations in Adélie penguin (Pygoscelis adeliae) egg membranes and chick feathers served as a proxy for Hg bioavailability in the marine environment surrounding the northern Antarctic Peninsula. Stable isotopes were measured in conjunction with Hg to infer information regarding feeding habits (δ15 N, diet/trophic level; δ13 C, foraging habitat). The Hg concentrations were low relative to toxicity benchmark values associated with adverse health effects in birds and ranged between 0.006 and 0.080 µg g-1 dry weight (n = 65) in egg membranes and 0.140 to 1.05 µg g-1 fresh weight (n = 38) in feathers. Egg membrane δ15 N signatures suggested that females from different breeding colonies had similar diets consisting of lower and higher trophic prey prior to arrival to breeding grounds. In contrast, δ15 N signatures in feathers indicated that chick diet varied by colony. The Hg concentrations demonstrated significant positive relationships with δ15 N, providing support for the hypothesis of Hg biomagnification up the food chain. The δ13 C signatures in both tissue types provided evidence of foraging habitat segregation among populations. The differences in Hg exposure and foraging ecology suggest that each colony has localized foraging behaviors by breeding adults that warrant additional investigation. Environ Toxicol Chem 2021;40:2791-2801. © 2021 SETAC.

Carbon isotopes of n-alkanoic acids in Antarctic ornithogenic sediments as indicators of sedimentary lipid sources and paleocological change.

Sedimentary n-alkanoic acids are ubiquitous in the environment and their carbon isotopic composition is increasingly used to identify the source of organic matter and to reconstruct past climatic and ecological changes. Here we investigate the distribution and carbon isotope ratios of n-alkanoic acids in two sediment profiles influenced by animal excrement in Antarctica. We found that organic matter input from animal excrement is the predominate source of short- and mid-chain n-alkanoic acids in the ornithogenic sediments. Decreased δ13C values are closely related to increased excrement input of penguins and seals that occupied the study site, especially in C16n-alkanoic acid. Long-chain (>C24) n-alkanoic acids likely originate from moss and heterotrophic microbes, and the δ13C values of C26n-alkanoic acid were consistent with organic biomarkers and bio-elements from animal excrement. Two possible processes are suggested to explain the close relationship between C26n-alkanoic acid δ13C values and animal excrement input. All the results indicate that the carbon isotopes of n-alkanoic acids in ornithogenic sediments can be used to indicate historical population change of penguins or seals in Antarctica.

Application of δ15N to trace the impact of penguin guano on terrestrial and aquatic nitrogen cycles in Victoria Land, Ross Sea region, Antarctica.

Penguin colonies in Antarctica offer an ideal "natural laboratory" to investigate ecosystem function and the nitrogen (N) cycle. This study assessed the spatial distribution of penguin-derived N from guano and quantitatively assessed its impact on plant N utilization strategies in Victoria Land, Ross Sea region, Antarctica. Soil, moss, and aquatic microbial mats were collected inside and outside an active Adélie penguin (Pygoscelis adeliae) colony and analyzed for δ15N of total and inorganic nitrogen (NH4+-N and NO3--N). The soil total nitrogen (TN), NH4+-N, and NO3--N concentrations, as well as their δ15N values were significantly higher in guano-impacted areas than those in guano-free areas, verifying that guano is an important N source at and near penguin colonies. However, even far from the penguin colonies, soil δ15N values resembled those in penguin colonies, suggesting strong spatial impacts of penguin-derived N. The moss impacted by guano was more enriched in δ15N than in guano-free areas. The δ15N values of NH4+-N and NO3--N in soils covered with moss revealed that the moss might prefer inorganic N in the absence of guano, while the dissolved organic N would become an important source for moss growing on ornithogenic soils. Aquatic microbial mat samples near penguin colonies were 15N-enriched, but 15N-depleted at upland sites.

The rise and fall of an ancient Adélie penguin 'supercolony' at Cape Adare, Antarctica.

We report new discoveries and radiocarbon dates on active and abandoned Adélie penguin (Pygoscelis adeliae) colonies at Cape Adare, Antarctica. This colony, first established at approximately 2000 BP (calendar years before present, i.e. 1950), is currently the largest for this species with approximately 338 000 breeding pairs, most located on low-lying Ridley Beach. We hypothesize that this colony first formed after fast ice began blocking open-water access by breeding penguins to the Scott Coast in the southern Ross Sea during a cooling period also at approximately 2000 BP. Our results suggest that the new colony at Cape Adare continued to grow, expanding to a large upper terrace above Ridley Beach, until it exceeded approximately 500 000 breeding pairs (a 'supercolony') by approximately 1200 BP. The high marine productivity associated with the Ross Sea polynya and continental shelf break supported this growth, but the colony collapsed to its present size for unknown reasons after approximately 1200 BP. Ridley Beach will probably be abandoned in the near future due to rising sea level in this region. We predict that penguins will retreat to higher elevations at Cape Adare and that the Scott Coast will be reoccupied by breeding penguins as fast ice continues to dissipate earlier each summer, restoring open-water access to beaches there.

Differing foraging strategies influence mercury (Hg) exposure in an Antarctic penguin community.

Seabirds are ideal model organisms to track mercury (Hg) through marine food webs as they are long-lived, broadly distributed, and are susceptible to biomagnification due to foraging at relatively high trophic levels. However, using these species as biomonitors requires a solid understanding of the degree of species, sexual and age-specific variation in foraging behaviors which act to mediate their dietary exposure to Hg. We combined stomach content analysis along with Hg and stable isotope analyses of blood, feathers and common prey items to help explain inter and intra-specific patterns of dietary Hg exposure across three sympatric Pygoscelis penguin species commonly used as biomonitors of Hg availability in the Antarctic marine ecosystem. We found that penguin tissue Hg concentrations differed across species, between adults and juveniles, but not between sexes. While all three penguins species diets were dominated by Antarctic krill (Euphausia superba) and to a lesser extent fish, stable isotope based proxies of relative trophic level and krill consumption could not by itself sufficiently explain the observed patterns of inter and intra-specific variation in Hg. However, integrating isotopic approaches with stomach content analysis allowed us to identify the relatively higher risk of Hg exposure for penguins foraging on mesopelagic prey relative to congeners targeting epipelagic or benthic prey species. When possible, future seabird biomonitoring studies should seek to combine isotopic approaches with other, independent measures of foraging behavior to better account for the confounding effects of inter and intra-specific variation on dietary Hg exposure.

Levels of Mercury in Feathers of Clapper Rails (Rallus crepitans) over 45 Years in Coastal Salt Marshes of New Hanover County, North Carolina.

We sampled clapper rail (Rallus crepitans) feathers from museum specimens collected between 1965 and 2010 to investigate changes in mercury (Hg) availability in coastal marshes of New Hanover County, North Carolina. Stable isotope analysis (δ(13)C and δ(15)N) was conducted to control for dietary shifts that may have influenced Hg exposure. Hg concentrations ranged from 0.96 to 9.22 µg/g (ppm), but showed no significant trend over time; diet (δ(15)N) or foraging habitat (δ(13)C) also provided little to no explanatory power to the variation in Hg concentrations among clapper rails. Our findings suggest the bioavailability of Hg to clapper rails in coastal North Carolina salt marshes has remained consistent over time, despite the global trend of increasing mercury in many other bird species, providing an excellent baseline for any future assessment of Hg availability to salt marsh birds in coastal North Carolina.

Radionuclides in ornithogenic sediments as evidence for recent warming in the Ross Sea region, Antarctica.

Radionuclides including (210)Pb, (226)Ra and (137)Cs were analyzed in eight ornithogenic sediment profiles from McMurdo Sound, Ross Sea region, East Antarctica. Equilibration between (210)Pb and (226)Ra were reached in all eight profiles, enabling the determination of chronology within the past two centuries through the Constant Rate of Supply (CRS) model. Calculated fluxes of both (210)Pb and (137)Cs varied drastically among four of the profiles (MB4, MB6, CC and CL2), probably due to differences in their sedimentary environments. In addition, we found the flux data exhibiting a clear decreasing gradient in accordance with their average deposition rate, which was in turn related to the specific location of the profiles. We believe this phenomenon may correspond to global warming of the last century, since warming-induced surface runoff would bring more inflow water and detritus to the coring sites, thus enhancing the difference among the profiles. To verify this hypothesis, the deposition rate against age of the sediments was calculated based on their determined chronology, which showed ascending trends in all four profiles. The significant increase in deposition rates over the last century is probably attributable to recent warming, implying a potential utilization of radionuclides as environmental indicators in this region.

Distribution patterns and possible influencing factors of As speciation in ornithogenic sediments from the Ross Sea region, East Antarctica.

Ornithogenic sediments are rich in toxic As (arsenic) compounds, posing a potential threat to local ecosystems. Here we analyzed the distribution of As speciation in three ornithogenic sediment profiles (MB6, BI and CC) collected from the Ross Sea region, East Antarctica. The distributions of total As and total P (phosphorus) concentrations were highly consistent in all three profiles, indicating that guano input is a major factor controlling total As distribution in the ornithogenic sediments. The As found in MB6 and CC is principally As(V) (arsenate), in BI As(III) (arsenite) predominates, but the As in fresh guano is largely composed of DMA (dimethylarsinate). The significant difference of As species between fresh guano and ornithogenic sediment samples may be related to diagenetic processes after deposition by seabirds. Based on analysis of the sedimentary environment in the studied sediments, we found that the redox conditions have an obvious influence on the As speciation distribution. Moreover, the distributions of As(III) and chlorophyll a in the MB6 and BI profiles are highly consistent, demonstrating that aquatic algae abundance may also influence the distribution patterns of As speciation in the ornithogenic sediments.

Chronic mercury exposure in Late Neolithic/Chalcolithic populations in Portugal from the cultural use of cinnabar.

Cinnabar is a natural mercury sulfide (HgS) mineral of volcanic or hydrothermal origin that is found worldwide. It has been mined prehistorically and historically in China, Japan, Europe, and the Americas to extract metallic mercury (Hg(0)) for use in metallurgy, as a medicinal, a preservative, and as a red pigment for body paint and ceramics. Processing cinnabar via combustion releases Hg(0) vapor that can be toxic if inhaled. Mercury from cinnabar can also be absorbed through the gut and skin, where it can accumulate in organs and bone. Here, we report moderate to high levels of total mercury (THg) in human bone from three Late Neolithic/Chalcolithic (5400-4100 B.P.) sites in southern Portugal that were likely caused by cultural use of cinnabar. We use light stable isotope and Hg stable isotope tracking to test three hypotheses on the origin of mercury in this prehistoric human bone. We traced Hg in two individuals to cinnabar deposits near Almadén, Spain, and conclude that use of this mineral likely caused mild to severe mercury poisoning in the prehistoric population. Our methods have applications to bioarchaeological investigations worldwide, and for tracking trade routes and mobility of prehistoric populations where cinnabar use is documented.

Fractionation distribution and preliminary ecological risk assessment of As, Hg and Cd in ornithogenic sediments from the Ross Sea region, East Antarctica.

To evaluate mobility of toxic elements and their potential ecological risk caused by seabird biovectors, the fractionation distributions of arsenic (As), mercury (Hg) and cadmium (Cd) were investigated in three ornithogenic sediment profiles from the Ross Sea region, East Antarctica. The results show residual As holds a dominant position, and Hg mainly derives from residual, organic matter-bound and humic acid-bound fractions, indicating weak mobility of As and Hg. However, exchangeable Cd occupies a considerable proportion in studied samples, suggesting Cd has strong mobility. The preliminary evaluation of Sediment Quality Guidelines (SGQs) shows adverse biological effects may occur occasionally for As and Cd, and rarely for Hg. Using Risk Assessment Code (RAC), the ecological risk is assessed at moderate, low and very high for As, Hg and Cd pollution, respectively. Organic matter derived from guano is the main factor controlling the mobility of Hg and Cd through adsorption and complexation.

From warm to cold: migration of Adélie penguins within Cape Bird, Ross Island.

Due to their sensitivity to environmental change, penguins in Antarctica are widely used as bio-indicators in paleoclimatic research. On the basis of bio-element assemblages identified in four ornithogenic sediment profiles, we reconstructed the historical penguin population change at Cape Bird, Ross Island, for the past 1600 years. Clear succession of penguin population peaks were observed in different profiles at about 1400 AD, which suggested a high probability of migration within this region. The succession was most obviously marked by a sand layer lasting from 1400 to 1900 AD in one of the analyzed profiles. Multiple physical/chemical parameters indicated this sand layer was not formed in a lacustrine environment, but was marine-derived. Both isostatic subsidence and frequent storms under the colder climatic condition of the Little Ice Age were presumed to have caused the abandonment of the colonies, and we believe the penguins migrated from the coastal area of mid Cape Bird northward and to higher ground as recorded in the other sediment profiles. This migration was an ecological response to global climate change and possible subsequent geological effects in Antarctica.

A comprehensive assessment of mercury exposure in penguin populations throughout the Southern Hemisphere: Using trophic calculations to identify sources of population-level variation.

The wide geographic distribution of penguins (Order Sphenisciformes) throughout the Southern Hemisphere provided a unique opportunity to use a single taxonomic group as biomonitors of mercury among geographically distinct marine ecosystems. Mercury concentrations were compared among ten species of penguins representing 26 geographically distinct breeding populations. Mercury concentrations were relatively low (⩽2.00ppm) in feathers from 18/26 populations considered. Population-level differences in trophic level explained variation in mercury concentrations among Little, King, and Gentoo penguin populations. However, Southern Rockhopper and Magellanic penguins breeding on Staten Island, Tierra del Fuego, had the highest mercury concentrations relative to their conspecifics despite foraging at a lower trophic level. The concurrent use of stable isotope and mercury data allowed us to document penguin populations at the greatest risk of exposure to harmful concentrations of mercury as a result of foraging at a high trophic level or in geographic 'hot spots' of mercury availability.

Multi-tissue analyses reveal limited inter-annual and seasonal variation in mercury exposure in an Antarctic penguin community.

Inter-annual variation in tissue mercury concentrations in birds can result from annual changes in the bioavailability of mercury or shifts in dietary composition and/or trophic level. We investigated potential annual variability in mercury dynamics in the Antarctic marine food web using Pygoscelis penguins as biomonitors. Eggshell membrane, chick down, and adult feathers were collected from three species of sympatrically breeding Pygoscelis penguins during the austral summers of 2006/2007-2010/2011. To evaluate the hypothesis that mercury concentrations in penguins exhibit significant inter-annual variation and to determine the potential source of such variation (dietary or environmental), we compared tissue mercury concentrations with trophic levels as indicated by δ(15)N values from all species and tissues. Overall, no inter-annual variation in mercury was observed in adult feathers suggesting that mercury exposure, on an annual scale, was consistent for Pygoscelis penguins. However, when examining tissues that reflected more discrete time periods (chick down and eggshell membrane) relative to adult feathers, we found some evidence of inter-annual variation in mercury exposure during penguins' pre-breeding and chick rearing periods. Evidence of inter-annual variation in penguin trophic level was also limited suggesting that foraging ecology and environmental factors related to the bioavailability of mercury may provide more explanatory power for mercury exposure compared to trophic level alone. Even so, the variable strength of relationships observed between trophic level and tissue mercury concentrations across and within Pygoscelis penguin species suggest that caution is required when selecting appropriate species and tissue combinations for environmental biomonitoring studies in Antarctica.