Calibration of the pH-δ11B and temperature-Mg/Li proxies in the long-lived high-latitude crustose coralline red alga Clathromorphum compactum via controlled laboratory experiments

Abstract

A solid understanding of global oceanic change throughout Holocene time is needed to contextualize and interpret recent observations of rapid warming (Moore, 2016), ocean acidification (Popova et al., 2014; Qi et al., 2017), increasing meltwater input (Halfar et al., 2013; Notz and Stroeve, 2016) and circulation changes (Liu et al., 2017; Rahmstorf et al., 2015; Yang et al., 2016) in the Arctic and subarctic Oceans. Precisely reconstructing acidification and temperature variations throughout the Holocene will provide a vital context for interpreting current environmental changes and future climate projections in the region. However, existing paleoenvironmental reconstructions are sparse and uncertain, largely owing to limited availability of high fidelity paleoceanographic archives, such as marine carbonates, in high latitude waters. Coralline algae of the genus Clathromorphum have emerged as key candidates for reconstructing high-latitude environmental variability at annual to sub-annual resolution. Here, we present the first empirical calibrations of boron isotope-pH and Mg/Li-temperature relationships within the long-lived, crustose coralline red alga Clathromorphum compactum. Calibration experiments were performed in triplicate, growing wild-collected specimens for four months at three controlled temperatures (6.4 – 12.4 oC) and four pCO2 conditions (352 - 3230 ppm), to test the effects of these environmental parameters on the isotopic and elemental composition of the algal skeleton. We find that boron isotopes within the skeleton of C. compactum (δ11Bcc) are well correlated with δ11B of seawater borate (δ11Βborate), defining the following equation: δ11Βcc (2σ) = 1.46 (0.06) δ11Βborate + 6.91 (0.72). This equation can be used to reconstruct δ11Βborate of the coralline alga’s ambient seawater, from which past seawater pH can be calculated. We also identified a strong correlation between skeletal Mg/Li ratio and seawater temperature, defined by the equation: Mg/Li (2σ) = 0.17 (0.02) temperature (oC) + 1.02 (0.16). Therefore, despite the strong biological control that this species appears to exert on calcification site pH (elevated 1.0-1.6 pH units above seawater pH, inferred from δ11Bcc > δ11Βborate), and the apparent relationship between skeletal extension rate and skeletal Li/Ca and Mg/Ca, the δ11Bcc and Mg/Li ratios of the coralline alga’s skeleton strongly and significantly respond to ambient seawater pH and temperature, respectively. These results support the use of δ11B and Mg/Li within C. compactum for pH and temperature reconstructions of northern high-latitude oceans.