Julie Trotter

Did Cooling Oceans Trigger Ordovician Biodiversification? Evidence from Conodont Thermometry

The Ordovician Period, long considered a supergreenhouse state, saw one of the greatest radiations of life in Earths history. Previous temperature estimates of up to ∼70°C have spawned controversial speculation that the oxygen isotopic composition of seawater must have evolved over geological time. We present a very different global climate record determined by ion microprobe oxygen isotope analyses of Early Ordovician–Silurian conodonts. This record shows a steady cooling trend through the Early Ordovician reaching modern equatorial temperatures that were sustained throughout the Middle and Late Ordovician. This favorable climate regime implies not only that the oxygen isotopic composition of Ordovician seawater was similar to that of today, but also that climate played an overarching role in promoting the unprecedented increases in biodiversity that characterized this period.

Coral calcifying fluid pH dictates response to ocean acidification

Ocean acidification driven by rising levels of CO2 impairs calcification, threatening coral reef growth. Predicting how corals respond to CO2 requires a better understanding of how calcification is controlled. Here we show how spatial variations in the pH of the internal calcifying fluid (pHcf) in coral (Stylophora pistillata) colonies correlates with differential sensitivity of calcification to acidification. Coral apexes had the highest pHcf and experienced the smallest changes in pHcf in response to acidification. Lateral growth was associated with lower pHcf and greater changes with acidification. Calcification showed a pattern similar to pHcf, with lateral growth being more strongly affected by acidification than apical. Regulation of pHcf is therefore spatially variable within a coral and critical to determining the sensitivity of calcification to ocean acidification.

Comparison of dermal absorption of zinc from different sunscreen formulations and differing UV exposure based on stable isotope tracing.

In a pilot study to determine if zinc (Zn) from zinc oxide nanoparticles in sunscreen can penetrate human skin in vivo, nanoparticles (~30nm) of a stable isotope (52% (68)Zn enrichment) were incorporated into an essentially phytochemical-based formulation and applied to the backs of 3 human subjects twice daily for 5 days during the Southern Hemisphere winter. Blood and urine were collected prior to application and at regular intervals and up to 50 days. As observed in a larger outdoor trial following this pilot study but with a different formulation and with UV exposure: values of (68)Zn in blood continued to increase beyond the 5 day application phase with the highest measurement at 14 days after the first application; variable amounts of the (68)Zn tracer were observed in urine; and the amounts of extra Zn added to blood were small and indicate very low levels of absorption (minimal estimate <0.01% of the applied dose) through the skin. Reasons for differences in absorption detected in the stable isotope trials and previous investigations include: the sensitivity of the stable isotope method; the duration of the investigations; the number of applications of sunscreen formulation; in vitro methods with excised skin; lack of measurement of blood and urine; no skin flexing; and lack of UV exposure.

Rapid, high‐precision measurements of boron isotopic compositions in marine carbonates

RATIONALE The isotopic composition and elemental abundance of boron (B) in marine carbonates provide a powerful tool for tracking changes in seawater pH and carbonate chemistry. Progress in this field has, however, been hampered by the volatile nature of B, its persistent memory, and other uncertainties associated with conventional chemical extraction and mass spectrometric measurements. Here we show that for marine carbonates, these limitations can be overcome by using a simplified, low-blank, chemical extraction technique combined with robust multi-collector inductively couple plasma mass spectrometry (MC-ICPMS) methods. METHODS Samples are dissolved in dilute HNO3 and loaded first onto on a cation-exchange column with the major cations (Ca, Mg, Sr, Na) being quantitatively retained while the B fraction is carried in the eluent. The eluent is then passed directly through an anion column ensuring that any residual anions, such as SO4(2-), are removed. Isotopic measurements of (11)B/(10)B ratios are undertaken by matching both the B concentration and the isotopic compositions of the samples with the bracketing standard, thereby minimising corrections for cross-contamination. RESULTS The veracity of the MC-ICPMS procedure is demonstrated using a gravimetrically prepared laboratory standard, UWA24.7, relative to the international reference standard NIST SRM 951 (δ(11)B = 0‰). This gives values consistent with gravimetry (δ(11)B = 24.7 ± 0.3‰ 2sd) for solutions ranging in concentration from 50 to 500 ppb, equivalent to ~2-10 mg size coral samples. The overall integrity of the method for carbonate analysis is demonstrated by measurements of the international carbonate standard JCp-1 (δ(11)B = 24.3 ± 0.34‰ 2sd). CONCLUSIONS A streamlined, integrated approach is described here that enables rapid, accurate, high-precision measurements of boron isotopic compositions and elemental abundances in commonly analysed biogenic carbonates, such as corals, bivalves, and large benthic forams. The overall simplicity of this robust approach should greatly facilitate the wider application of boron isotope geochemistry, especially to marine carbonates.

pH homeostasis during coral calcification in a free ocean CO2 enrichment (FOCE) experiment, Heron Island reef flat, Great Barrier Reef.

Significance In situ free ocean CO2 enrichment (FOCE) experiments and geochemical analyses (δ11B, Sr/Ca) conducted on corals (Porites cylindrica) from the highly dynamic Heron Island reef flat of the Great Barrier Reef show that this species exerts strong physiological controls on the pH of their calcifying fluid (pHcf). Over an ∼6-mo period, from mid-winter to early summer, we show that these corals maintained their pHcf at near constant elevated levels independent of the highly variable temperatures and FOCE-controlled carbonate chemistries to which they were exposed, implying they have a high degree of tolerance to ocean acidification. Geochemical analyses (δ11B and Sr/Ca) are reported for the coral Porites cylindrica grown within a free ocean carbon enrichment (FOCE) experiment, conducted on the Heron Island reef flat (Great Barrier Reef) for a 6-mo period from June to early December 2010. The FOCE experiment was designed to simulate the effects of CO2-driven acidification predicted to occur by the end of this century (scenario RCP4.5) while simultaneously maintaining the exposure of corals to natural variations in their environment under in situ conditions. Analyses of skeletal growth (measured from extension rates and skeletal density) showed no systematic differences between low-pH FOCE treatments (ΔpH = ∼−0.05 to −0.25 units below ambient) and present day controls (ΔpH = 0) for calcification rates or the pH of the calcifying fluid (pHcf); the latter was derived from boron isotopic compositions (δ11B) of the coral skeleton. Furthermore, individual nubbins exhibited near constant δ11B compositions along their primary apical growth axes (±0.02 pHcf units) regardless of the season or treatment. Thus, under the highly dynamic conditions of the Heron Island reef flat, P. cylindrica up-regulated the pH of its calcifying fluid (pHcf ∼8.4–8.6), with each nubbin having near-constant pHcf values independent of the large natural seasonal fluctuations of the reef flat waters (pH ∼7.7 to ∼8.3) or the superimposed FOCE treatments. This newly discovered phenomenon of pH homeostasis during calcification indicates that coral living in highly dynamic environments exert strong physiological controls on the carbonate chemistry of their calcifying fluid, implying a high degree of resilience to ocean acidification within the investigated ranges.

Oxygen isotopic evidence for Late Triassic monsoonal upwelling in the northwestern Tethys

The oxygen isotopic composition of conodonts from the Pizzo Mondello section in the Sicani Basin (Sicily, Italy), on the northwestern Tethys margin, has been used to reconstruct regional paleoseawater conditions. The δ 18 O phos values (21‰–21.9‰) measured by sensitive high-resolution ion microprobe (SHRIMP II) are consistent with previously published δ 18 O phos data from the contemporaneous marginal Hallstatt-Meliata Basin (20.3‰–22.5‰) located farther north, but are distinctly higher than those previously reported from the open ocean setting of the nearby Lagonegro Basin (18.7‰–20.0‰). This ∼2‰ offset represents a temperature differential of ∼8 °C, suggesting that sea-surface temperatures along the northwestern margin (Sicani and Hallstatt-Meliata basins) of the Tethys Ocean were lower than in the open ocean (Lagonegro Basin) during the late Carnian (Tuvalian 2) to early Norian (Lacian). We interpret the cooler waters of the marginal basins to reflect coastal upwelling driven by strong monsoonal systems, as predicted by existing paleoclimate models for this region.

Coral calcification in a changing World and the interactive dynamics of pH and DIC upregulation

Coral calcification is dependent on the mutualistic partnership between endosymbiotic zooxanthellae and the coral host. Here, using newly developed geochemical proxies (δ11B and B/Ca), we show that Porites corals from natural reef environments exhibit a close (r2 ∼0.9) antithetic relationship between dissolved inorganic carbon (DIC) and pH of the corals’ calcifying fluid (cf). The highest DICcf (∼ × 3.2 seawater) is found during summer, consistent with thermal/light enhancement of metabolically (zooxanthellae) derived carbon, while the highest pHcf (∼8.5) occurs in winter during periods of low DICcf (∼ × 2 seawater). These opposing changes in DICcf and pHcf are shown to maintain oversaturated but stable levels of carbonate saturation (Ωcf ∼ × 5 seawater), the key parameter controlling coral calcification. These findings are in marked contrast to artificial experiments and show that pHcf upregulation occurs largely independent of changes in seawater carbonate chemistry, and hence ocean acidification, but is highly vulnerable to thermally induced stress from global warming.

Environmental constraints on Holocene cold-water coral reef growth off Norway: Insights from a multiproxy approach

High-latitude cold-water coral (CWC) reefs are particularly susceptible due to enhanced CO2 uptake in these regions. Using precisely dated (U/Th) CWCs (Lophelia pertusa) retrieved during research cruise POS 391 (Lopphavet 70.6°N, Oslofjord 59°N) we applied boron isotopes (δ11B), Ba/Ca, Li/Mg and U/Ca ratios to reconstruct the environmental boundary conditions of CWC reef growth. The sedimentary record from these CWC reefs reveals a lack of corals between ∼ 6.4 and 4.8 ka. The question remains if this phenomenon is related to changes in the carbonate system or other causes. The initial postglacial setting had elevated Ba/Ca ratios, indicative of meltwater fluxes showing a decreasing trend towards cessation at 6.4 ka with a oscillation pattern similar to continental glacier fluctuations. Downcore U/Ca ratios reveal an increasing trend, which is outside the range of modern U/Ca variability in L. pertusa, suggesting changes of seawater pH near 6.4 ka. The reconstructed BWT at Lopphavet reveals a striking similarity to Barent Sea-Surface and sub-Sea-Surface-Temperature records. We infer that meltwater pulses weakened the North Atlantic Current system resulting in southward advances of cold and CO2 rich Arctic waters. A corresponding shift in the δ11B record from ∼ 25.0‰ to ∼ 27.0 ‰ probably implies enhanced pH-up regulation of the CWCs due to the higher pCO2 concentrations of ambient seawater, which hastened Mid-Holocene CWC reef decline on the Norwegian Margin.

Boron Isotopic Systematics in Scleractinian Corals and the Role of pH Up-regulation

The boron isotopic composition (δ11B) of scleractinian corals has been used to track changes in seawater pH and more recently as a probe into the processes controlling bio-calcification. For corals that precipitate aragonite skeletons, up-regulation of pH appears to be a general characteristic, typically being ~0.3 to ~0.6 pH units higher than ambient seawater. The relationship between the pH of the corals calcifying-fluid (pHcf) and seawater pHT (total scale) is shown to be dependent on both physiological as well environmental factors. In laboratory experiments conducted on symbiont-bearing (zooxanthellate) corals under conditions of constant temperature and seawater pH, changes in the δ11B derived calcifying fluid pHcf is typically 1/3 to 1/2 of that of ambient seawater. Similar linear relationships are found for cold water corals that live in relatively stable, cold, deep-water environments but at significantly elevated levels of pHcf (~0.5–1 pH units above seawater), a likely response to the lower pH of their deep-sea environments. In contrast, zooxanthellae-bearing corals living in shallow-water reef environments that experience significant natural variations in temperature, light, nutrients and seawater pH, show different types of responses. For example, over seasonal time-scales Porites corals from the Great Barrier Reef (GBR) have a large range in pHcf of ~8.3 to ~8.5, significantly greater (~×2 to ~×3) than that of reef-water (pHT ~8.01 to ~8.08), and an order of magnitude greater than that expected from ‘static’ laboratory experiments. Strong physiological controls, but of a different character, are found in corals grown in a Free Ocean Carbon Enrichment Experiment (FOCE) conducted in situ within the Heron Island lagoon (GBR). These corals exhibit near constant pHcf values regardless of external changes in temperature and seawater pH. This pattern of strong physiologically controlled ‘pH-homeostasis’, with elevated but constant pHcf has been found despite large natural seasonal variations in the pH (±0.15 pH units) of the lagoon waters, as well as the even larger super-imposed decreases in seawater pH (~0.25 pH units) designed to simulate year 2100 conditions. In natural reef environments we thus find that the processes influencing the up-regulation of pHcf in symbiont-bearing corals are subject to strong physiological controls, behaviour that is not well simulated in the current generation of aquaria-based experiments with fixed seawater pH and temperature. Conversely, cold-water corals that lack symbionts and inhabit the relatively stable deep-sea environments hold the best prospects for providing reliable reconstructions of seawater pH. Clearly, further studies utilising the δ11B-pHcf proxy combined with other DIC/carbonate-ion proxies (e.g. B/Ca), but conducted under realistic ‘natural’ conditions, are required to elucidate the processes controlling coral bio-calcification and to better understand the vulnerability of scleractinian corals to anthropogenic driven warming and ocean acidification.

Source and supply of sediment to a shoreline salient in a fringing reef environment: Reef to shoreline sediment connections

Reef-associated landforms are coupled to the health of the reef ecosystem which produces the sediment that forms and maintains these landforms. However, this connection can make reef-fronted coastlines sensitive to the impacts of climate change, given that any decline in ecosystem health (e.g. decreasing sediment supply) or changes to physical processes (e.g. sea level rise, increasing wave energy) could drive the sediment budgets of these systems into a net erosive state. Therefore, knowledge of both the sediment sources and transport mechanisms is required to predict the sensitivity of reef-associated landforms to future climate change. Here, we examine the benthic habitat composition, sediment characteristics (composition, texture, and age), and transport mechanisms and pathways to understand the interconnections between coastal morphology and the reef system at Tantabiddi, Ningaloo Reef, Western Australia. Benthic surveys and sediment composition analysis revealed that although live coral accounts for less than 5% of the benthic cover, coral is the dominant sediment constituent (34% on average). Sediment ages (U/Th) were mostly found to be thousands of years old, suggesting that the primary sediment source is relic reef material (e.g. Holocene reef framework). Sediment transport across the lagoon was quantified through measurements of ripple migration rates, which were found to be shoreward migrating and responsible for feeding the large shoreline salient in the lee of the reef. The derived sediment fluxes were comparable with previously measured rates of sediment production by bioerosion. These results suggest that sediment budgets of systems dependent on old (>10 years) source materials may be more resilient to climate change as present-day reef health and community composition (i.e. sources of ‘new’ carbonate production) have limited influence on sediment supply. Therefore, the vulnerability of reef-associated landforms in these systems will be dictated by future changes to mechanisms of sediment generation (e.g. bioerosion) and/or physical processes.