ALBERT

Description: Lithium has proven a powerful tracer of weathering processes and chemical seawater evolution. Skeletal components of marine calcifying organisms, and in particular brachiopods, present promising archives of Li signatures. However, Li incorporation mechanisms and potential influence from biological processes or environmental conditions require a careful assessment. In order to constrain Li systematics in brachiopod shells, we present Li concentrations and isotope compositions for 11 calcitic brachiopod species collected from six different geographic regions, paralleled with data from culturing experiments where brachiopods were grown under varying environmental conditions and seawater chemistry (pH–pCO2, temperature, Mg/Ca ratio). The recent brachiopod specimens collected across different temperate and polar environments showed broadly consistent δ7Li values ranging from 25.2 to 28.1‰ (with mean δ7Li of 26.9 ± 1.5‰), irrespective of taxonomic rank, indicating that incorporation of Li isotopes into brachiopod shells is not strongly affected by vital effects related to differences among species. This results in Δ7Licalcite–seawater values (per mil difference in 7Li/6Li between brachiopod calcite shell and seawater) from −2.9‰ to −5.8‰ (with mean Δ7Licalcite–seawater value of −3.6‰), which is larger than the Δ7Licalcite–seawater values calculated based on data from planktonic foraminifera (~0‰ to ~−4‰). This range of values is further supported by results from brachiopods cultured experimentally. Under controlled culturing conditions simulating the natural marine environment, the Δ7Licalcite–seawater for Magellania venosa was −2.5‰ and not affected by an increase in temperature from 10 to 16 °C. In contrast, a decrease in Mg/Ca (or Li/Ca) ratio of seawater by addition of CaCl2 as well as elevated pCO2, and hence low-pH conditions, resulted in an increased Δ7Licalcite-seawater up to −4.6‰. Collectively, our results indicate that brachiopods represent valuable archives and provide an envelope for robust Li-based reconstruction of seawater evolution over the Phanerozoic.

Description: In the last few decades and in the near future CO2-induced ocean acidification is potentially a big threat to marine calcite-shelled animals (e.g. brachiopods, bivalves, corals and gastropods). Despite the great number of studies focusing on the effects of acidification on shell growth, metabolism, shell dissolution and shell repair, the consequences for biomineral formation remain poorly understood. Only a few studies have addressed the impact of ocean acidification on shell microstructure and geochemistry. In this study, a detailed microstructure and stable isotope geochemistry investigation was performed on nine adult brachiopod specimens of Magellania venosa (Dixon, 1789). These were grown in the natural environment as well as in controlled culturing experiments under different pH conditions (ranging from 7.35 to 8.15 ± 0.05) over different time intervals (214 to 335 days). Details of shell microstructural features, such as thickness of the primary layer, density and size of endopunctae and morphology of the basic structural unit of the secondary layer were analysed using scanning electron microscopy. Stable isotope compositions (δ13C and δ18O) were tested from the secondary shell layer along shell ontogenetic increments in both dorsal and ventral valves. Based on our comprehensive dataset, we observed that, under low pH conditions, M. venosa produced a more organic-rich shell with higher density of and larger endopunctae, and smaller secondary layer fibres. Also, increasingly negative δ13C and δ18O values are recorded by the shell produced during culturing and are related to the CO2 source in the culture set-up. Both the microstructural changes and the stable isotope results are similar to observations on brachiopods from the fossil record and strongly support the value of brachiopods as robust archives of proxies for studying ocean acidification events in the geologic past.

Description: CO2-induced ocean acidification and associated decrease of seawater carbonate saturation state contributed to multiple environmental crises in Earth’s history, and currently poses a major threat for marine calcifying organisms. Owing to their high abundance and good preservation in the Phanerozoic geological record, brachiopods present an advantageous taxon of marine calcifiers for palaeo-proxy applications as well as studies on biological mechanism to cope with environmental change. To investigate the geochemical and physiological responses of brachiopods to prolonged low-pH conditions we cultured Magellania venosa, Terebratella dorsata and Pajaudina atlantica under controlled experimental settings over a period of more than two years. Our experiments demonstrate that brachiopods form their calcite shells under strong biological control, which enables them to survive and grow under low-pH conditions and even in seawater strongly undersaturated with respect to calcite (pH = 7.35, Ωcal = 0.6). Using boron isotope (δ11B) systematics including MC-ICP-MS as well as SIMS analyses, validated against in vivo microelectrode measurements, we show that this resilience is achieved by strict regulation of the calcifying fluid pH between the epithelial mantle and the shell. We provide a culture-based δ11B−pH calibration, which as a result of the internal pH regulatory mechanisms deviates from the inorganic borate ion to pH relationship, but confirms a clear yet subtle pH dependency for brachiopods. At a micro-scale level, the incorporation of boron appears to be principally driven by a physiological gradient across the shell, where the δ11B values of the innermost calcite record the internal calcifying fluid pH while the composition of the outermost layers is also influenced by seawater pH. These findings are of consequence to studies on biomineralisation processes, physiological adaptations as well as past climate reconstructions.

Description: Brachiopods present a key fossil group for Phanerozoic palaeo-environmental and palaeo-oceanographical reconstructions, owing to their good preservation and abundance in the geological record. Yet to date, hardly any geochemical proxies have been calibrated in cultured brachiopods and only little is known on the mechanisms that control the incorporation of various key elements into brachiopod calcite. To evaluate the feasibility and robustness of multiple Element/Ca ratios as proxies in brachiopods, specifically Li/Ca, B/Ca, Na/Ca, Mg/Ca, Sr/Ca, Ba/Ca, as well as Li/Mg, we cultured Magellania venosa, Terebratella dorsata and Pajaudina atlantica under controlled experimental settings over a period of more than two years with closely monitored ambient conditions, carbonate system parameters and elemental composition of the culture medium. The experimental setup comprised of two control aquariums (pH0 = 8.0 and 8.15, T = 10 °C) and treatments where pCO2 − pH (pH1 = 7.6 and pH2 = 7.35), temperature (T = 16 °C) and chemical composition of the culture medium were manipulated. Our results indicate that the incorporation of Li and Mg is strongly influenced by temperature, growth effects as well as carbonate chemistry, complicating the use of Li/Ca, Mg/Ca and Li/Mg ratios as straightforward reliable proxies. Boron partitioning varied greatly between the treatments, however without a clear link to carbonate system parameters or other environmental factors. The partitioning of both Ba and Na varied between individuals, but was not systematically affected by changes in the ambient conditions. We highlight Sr as a potential proxy for DIC, based on a positive trend between Sr partitioning and carbonate chemistry in the culture medium. To explain the observed dependency and provide a quantitative framework for exploring elemental variations, we devise the first biomineralisation model for brachiopods, which results in a close agreement between modelled and measured Sr distribution coefficients. We propose that in order to sustain shell growth under increased DIC, a decreased influx of Ca2+ to the calcifying fluid is necessary, driving the preferential substitution of Sr2+ for Ca2+ in the crystal lattice. Finally, we conducted micro-computed tomography analyses of the shells grown in the different experimental treatments. We present pore space – punctae – content quantification that indicates that shells built under increased environmental stress, and in particular elevated temperature, contain relatively more pore space than calcite, suggesting this parameter as a potential novel proxy for physiological stress and even environmental conditions.

Description: The loss of carbonate production during the Toarcian Oceanic Anoxic Event (T-OAE, ca. 183 Ma) is hypothesized to have been at least partly triggered by ocean acidification linked to magmatism from the Karoo-Ferrar large igneous province (southern Africa and Antarctica). However, the dynamics of acidification have never been directly quantified across the T-OAE. Here, we present the first record of temporal evolution of seawater pH spanning the late Pliensbachian and early Toarcian from the Lusitanian Basin (Portugal) reconstructed on the basis of boron isotopic composition (δ11B) of brachiopod shells. δ11B declines by ~1‰ across the Pliensbachian-Toarcian boundary (Pl-To) and attains the lowest values (~12.5‰) just prior to and within the T-OAE, followed by fluctuations and a moderately increasing trend afterwards. The decline in δ11B coincides with decreasing bulk CaCO3 content, in parallel with the two-phase decline in carbonate production observed at global scales and with changes in pCO2 derived from stomatal indices. Seawater pH had declined significantly already prior to the T-OAE, probably due to the repeated emissions of volcanogenic CO2. During the earliest phase of the T-OAE, pH increased for a short period, likely due to intensified continental weathering and organic carbon burial, resulting in atmospheric CO2 drawdown. Subsequently, pH dropped again, reaching the minimum in the middle of the T-OAE. The early Toarcian marine extinction and carbonate collapse were thus driven, in part, by ocean acidification, similar to other Phanerozoic events caused by major CO2 emissions and warming.

Description: Lakes and reservoirs play an important role in the carbon cycle, and therefore, monitoring their metabolic rates is essential. The triple oxygen isotope anomaly of dissolved O2 [17Δ = ln(1+δ17O) − 0.518×ln(1+δ18O)] offers a new, in situ, perspective on primary production, but is yet to be evaluated in freshwater systems. We investigated the 17Δ together with oxygen-argon ratio (δO2/Ar) in the subtropical Feitsui Reservoir in Taiwan from June 2014 to July 2015. Here, we present the seasonal variations in 17Δ, GP (gross production), NP (net production) and the NP/GP (net to gross ratio) in association with environmental parameters measured. The 17Δ varied with depth and season, with values ranging between 19 and 186 per meg. The 17Δ GP rates were lower from April to September averaging 215±93 mg C m−2 d−1 and higher from October to January averaging 523±66 mg C m−2 d−1. The estimated average annual 17Δ GP was 104 g C m−2 year−1 and the average annual NP was 22 g C m−2 year−1. Overall, the NP/ GP varied slightly between 0.02 and 0.36 and the reservoir was net autotrophic in the mixed layer. Comparisons between 17Δ GP rates and the production rates estimated by in vitro 14C bottle incubation method (14C GP) were consistent on the same order of magnitude, with the 17Δ GP/14C GP ratio of 1±0.8 throughout the study. Although typhoon occurrences were scarce, higher than average 17Δ values and 17Δ GP rates were recorded after typhoon events.

Description: Lakes and reservoirs play an important role in the carbon cycle, and therefore monitoring their metabolic rates is essential. The triple oxygen-isotope anomaly of dissolved O2 [17Δ =  ln(1+δ17O) − 0.518  ×  ln(1 + δ18O)] offers a new, in situ, perspective on primary production, yet little is known about 17Δ from freshwater systems. We investigated the 17Δ together with the oxygen : argon ratio [Δ(O2 ∕ Ar)] in the subtropical Feitsui Reservoir in Taiwan from June 2014 to July 2015. Here, we present the seasonal variations in 17Δ, GP (gross production), NP (net production) and the NP ∕ GP (net to gross ratio) in association with environmental parameters. The 17Δ varied with depth and season, with values ranging between 26 and 205 per meg. The GP rates were observed to be higher (702 ± 107 mg C m−2 d−1) in winter than those (303 ± 66 mg C m−2 d−1) recorded during the summer. The overall averaged GP was 220 g C m−2 yr−1 and NP was −3 g C m−2 yr−1, implying the reservoir was net heterotrophic on an annual basis. This is due to negative NP rates from October to February (−198 ± 78 mg C m−2 d−1). Comparisons between GP rates obtained from the isotope mass balance approach and 14C bottle incubation method (14C–GP) showed consistent values on the same order of magnitude with a GP ∕ 14C–GP ratio of 1.2 ± 1.1. Finally we noted that, although typhoon occurrences were scarce, higher than average 17Δ values and GP rates were recorded after typhoon events.