Within-Otolith Variability in Chemical Fingerprints: Implications for Sampling Designs and Possible Environmental Interpretation

Largely used as a natural biological tag in studies of dispersal/connectivity of fish, otolith elemental fingerprinting is usually analyzed by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). LA-ICP-MS produces an elemental fingerprint at a discrete time-point in the life of a fish and can generate data on within-otolith variability of that fingerprint. The presence of within-otolith variability has been previously acknowledged but not incorporated into experimental designs on the presumed, but untested, grounds of both its negligibility compared to among-otolith variability and of spatial autocorrelation among multiple ablations within an otolith. Here, using a hierarchical sampling design of spatial variation at multiple scales in otolith chemical fingerprints for two Mediterranean coastal fishes, we explore: 1) whether multiple ablations within an otolith can be used as independent replicates for significance tests among otoliths, and 2) the implications of incorporating within-otolith variability when assessing spatial variability in otolith chemistry at a hierarchy of spatial scales (different fish, from different sites, at different locations on the Apulian Adriatic coast). We find that multiple ablations along the same daily rings do not necessarily exhibit spatial dependency within the otolith and can be used to estimate residual variability in a hierarchical sampling design. Inclusion of within-otolith measurements reveals that individuals at the same site can show significant variability in elemental uptake. Within-otolith variability examined across the spatial hierarchy identifies differences between the two fish species investigated, and this finding leads to discussion of the potential for within-otolith variability to be used as a marker for fish exposure to stressful conditions. We also demonstrate that a 'cost'-optimal allocation of sampling effort should typically include some level of within-otolith replication in the experimental design. Our findings provide novel evidence to aid the design of future sampling programs and improve our general understanding of the mechanisms regulating elemental fingerprints.

A novel sub-seabed CO2 release experiment informing monitoring and impact assessment for geological carbon storage

Carbon capture and storage is a mitigation strategy that can be used to aid the reduction of anthropogenic CO2 emissions. This process aims to capture CO2from large point-source emitters and transport it to a long-term storage site. For much of Europe, these deep storage sites are anticipated to be sited below the sea bed on continental shelves. A key operational requirement is an understanding of best practice of monitoring for potential leakage and of the environmental impact that could result from a diffusive leak from a storage complex. Here we describe a controlled CO2release experiment beneath the seabed, which overcomes the limitations of laboratory simulations and natural analogues. The complex processes involved in setting up the experimental facility and ensuring its successful operation are discussed, including site selection, permissions, communications and facility construction. The experimental design and observational strategy are reviewed with respect to scientific outcomes along with lessons learnt in order to facilitate any similar future.