Ba/Ca of stylasterid coral skeletons records dissolved seawater barium concentrations

The concentration of dissolved barium in seawater ([Ba]SW) is influenced by both primary productivity and ocean circulation patterns. Reconstructing past subsurface [Ba]SW can therefore provide important information on processes which regulate global climate. Previous Ba/Ca measurements of scleractinian and bamboo deep-sea coral skeletons exhibit linear relationships with [Ba]SW, acting as archives for past Ba cycling. However, skeletal Ba/Ca ratios of the Stylasteridae – a group of widely distributed, azooxanthellate, hydrozoan coral – have not been previously studied. Here, we present Ba/Ca ratios of modern stylasterid (aragonitic, calcitic and mixed mineralogy) and azooxanthellate scleractinian skeletons, paired with published proximal hydrographic data. We find that [Ba]SW and sample mineralogy are the primary controls on stylasterid Ba/Ca, while seawater temperature exerts a weak secondary control. [Ba]SW also exerts a strong control on azooxanthellate scleractinian Ba/Ca. However, Ba-incorporation into scleractinian skeletons varies between locations and across depth gradients, and we find a more sensitive relationship between scleractinian Ba/Ca and [Ba]SW than previously reported. Paired Sr/Ca measurements suggest that this variability in scleractinian Ba/Ca may result from the influence of varying degrees of Rayleigh fractionation during calcification. We find that these processes exert a smaller influence on Ba-incorporation into stylasterid coral skeletons, a result consistent with other aspects of their skeletal geochemistry. Stylasterid Ba/Ca ratios are therefore a powerful, novel archive of past changes in [Ba]SW, particularly when measured in combination with temperature sensitive tracers such as Li/Mg or Sr/Ca. Indeed, with robust [Ba]SW and temperature proxies now established, stylasterids have the potential to be an important new archive for palaeoceanographic studies

Monitoring Mercury in the Loggerhead Sea Turtle, <i>Caretta caretta</i>

The validity of using blood samples and keratinized scutes for nonlethal routine monitoring of mercury (Hg) in loggerhead sea turtles, Caretta caretta, is evaluated in the context of how effectively these matrixes predict internal tissue Hg burdens and the different temporal scales of exposure they represent. Total Hg (THg) was measured in blood and scutes collected from live captures (n = 34) and liver, kidney, muscle, spinal cord, blood, and scutes collected from freshly stranded loggerhead turtles (n = 6) along the coast of the southeastern United States. Linear regressions between monitoring compartments and internal tissues from stranded animals were all statistically significant (r2 > 0.805, p < 0.015) but varied in their utility as a predictive tool depending on which tissues were paired. Blood was an effective predictor of THg in muscle (r2 = 0.988, p r2 = 0.988, p < 0.0001), while scute was the most accurate predictor of THg in liver (r2 = 0.948, p = 0.0010). The strength of the relationship between tissues types is believed to reflect the similarity in the temporal scales they represent and the variability in the fraction of methylmercury present. The stability of Hg in the scute matrix makes this tissue preferable for approximating long-term exposure, while blood Hg levels can be affected by recent changes in Hg intake. THg levels in blood and scutes from live captures were highly correlated (linear regression r2 = 0.926, p < 0.0001) and increased significantly with body mass (r2 = 0.173, p = 0.016 and r2 = 0.187, p = 0.012 respectively), further supporting that there is a component reflecting long-term accumulation of Hg in these matrixes. We also present a novel technique using the residuals from the blood-scute regression as an index of recent exposure (IRE). The interpretation of this value is derived from the comparison between the most recent Hg intake (which contributes to the Hg measured in the blood) relative to the average past intake (which is recorded in the scute). A stepwise multiple regression revealed a significant positive relationship between the IRE and the proximity of the capture site to the nearest major industrial river mouth (p = 0.0102). This suggests that there is an elevation of bioavailable Hg in nearshore habitats where terrestrial influences and anthropogenic impacts are high. Seasonal foraging site fidelity and the variability in environmental Hg may explain the high intraspecific variability and occasional highly contaminated turtle seen in this and previous studies

Evaluation of Sample Preparation Methods for the Analysis of Reef-Building Corals Using ¹H-NMR-Based Metabolomics

The field of metabolomics generally lacks standardized methods for the preparation of samples prior to analysis. This is especially true for metabolomics of reef-building corals, where the handful of studies that were published employ a range of sample preparation protocols. The utilization of metabolomics may prove essential in understanding coral biology in the face of increasing environmental threats, and an optimized method for preparing coral samples for metabolomics analysis would aid this cause. The current study evaluates three important steps during sample processing of stony corals: (i) metabolite extraction, (ii) metabolism preservation, and (iii) subsampling. Results indicate that a modified Bligh and Dyer extraction is more reproducible across multiple coral species compared to methyl tert-butyl ether and methanol extractions, while a methanol extraction is superior for feature detection. Additionally, few differences were detected between spectra from frozen or lyophilized coral samples. Finally, extraction of entire coral nubbins increased feature detection, but decreased throughput and was more susceptible to subsampling error compared to a novel tissue powder subsampling method. Overall, we recommend the use of a modified Bligh and Dyer extraction, lyophilized samples, and the analysis of brushed tissue powder for the preparation of reef-building coral samples for 1H NMR metabolomics

Morphological, elemental, and boron isotopic insights into pathophysiology of diseased coral growth anomalies

AbstractCoral growth anomalies (GAs) are tumor-like lesions that are detrimental to colony fitness and are commonly associated with high human population density, yet little is known about the disease pathology or calcification behavior. SEM imagery, skeletal trace elements and boron isotopes (δ11B) have been combined as a novel approach to study coral disease. Low Mg/Ca, and high U/Ca, Mo/Ca, and V/Ca potentially suggest a decreased abundance of “centers of calcification” and nitrogen-fixation in GAs. Estimates of carbonate system parameters from δ11B and B/Ca measurements indicate reduced pH (−0.05 units) and [CO32−] within GA calcifying fluid. We theorize GAs re-allocate resources away from internal pH upregulation to sustain elevated tissue growth, resulting in a porous and fragile skeleton. Our findings show that dystrophic calcification processes could explain structural differences seen in GA skeletons and highlight the use of skeletal geochemistry to shed light on disease pathophysiology in corals.</jats:p